EP2781259B1 - Composition absorbant l'eau et procédé pour sa production, ainsi que son procédé d'entreposage et de stockage - Google Patents

Composition absorbant l'eau et procédé pour sa production, ainsi que son procédé d'entreposage et de stockage Download PDF

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Publication number
EP2781259B1
EP2781259B1 EP12849458.0A EP12849458A EP2781259B1 EP 2781259 B1 EP2781259 B1 EP 2781259B1 EP 12849458 A EP12849458 A EP 12849458A EP 2781259 B1 EP2781259 B1 EP 2781259B1
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EP
European Patent Office
Prior art keywords
water absorbent
agent composition
water
absorbent resin
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP12849458.0A
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German (de)
English (en)
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EP2781259A1 (fr
EP2781259A4 (fr
Inventor
Manabu Ueda
Hiroyuki Ikeuchi
Yasuhisa Nakashima
Katsuyuki Wada
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Publication of EP2781259A4 publication Critical patent/EP2781259A4/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/40—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing ingredients of undetermined constitution or reaction products thereof, e.g. plant or animal extracts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • A61F2013/530708—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/44—Materials comprising a mixture of organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss

Definitions

  • the present invention relates to a water absorbent agent composition and a method for producing the water absorbent agent composition, as well as a method for storing and stocking the water absorbent agent composition.
  • the present invention relates to: a water absorbent agent composition which is applicable to sanitary goods such as paper diapers, sanitary napkins, and incontinence pads as a constituent thereof being less stressful to skin and having a stable deodorizing performance even after a long-term storage; a method for producing the water absorbent agent composition; as well as a method for storing and stocking the water absorbent agent composition.
  • a water absorbent resin is widely used as one of constituents (a main constituent) of sanitary goods (absorbent article) such as paper diapers, particularly paper diapers for aged adults, sanitary napkins, and incontinence pads, in order to absorb body fluids (urine or blood).
  • sanitary goods such as paper diapers, particularly paper diapers for aged adults, sanitary napkins, and incontinence pads, in order to absorb body fluids (urine or blood).
  • Such a water absorbent resin is required to have not only water absorbent performance such as a water absorption capacity (without load) (an amount of a liquid which can be absorbed and held by a water absorbent resin or water absorbent agent composition; a water absorbing capacity), a water absorption capacity under load, a water absorbent speed, and permeability, but also an additional function such as a deodorizing property, an antibacterial property, a low-coloring property, and prevention of a deterioration. So far, addition of compounds such as deodorants, antibacterial agents, aromatic substances, and coloring preventing agents to a water absorbent resin has been discussed.
  • Patent Literatures 1 to 29, 32, 33 etc. a water absorbent resin having an aromatic property is disclosed in Patent Literature 30 etc., and a water absorbent resin having an coloring preventing function is disclosed in Patent Literature 31.
  • the aforementioned patent literatures disclose deodorants and combinations of deodorants and antibacterial agents in order to provide a water absorbent resin with a deodorizing function or antibacterial function.
  • the aforementioned patent literatures disclose a water absorbent agent composition of an essence extracted from leaves of Theaceae plants and a water absorbent resin (Patent Literature 1), a water absorbent agent composition of an essence extracted from conifers and a water absorbent resin having a specific performance (e.g.
  • Patent Literature 2 discontinuous absorption capacity under load performance
  • Patent Literature 3 a water absorbent agent composition in which zeolite powder is dispersed inside a water absorbent resin
  • Patent Literature 3 a long-acting antibacterial deodorant containing a Japanese horseradish extract, a mustard extract or the like, a maintaining agent (absorbent gelatinizer) for maintaining an antibacterial and deodorizing effect
  • Patent Literature 4 a deodorant and antibacterial water absorbing agent (composition) containing a compound having an antibacterial function against ammonia-producing bacteria etc. and a water absorbent resin
  • Patent Literature 5 a water absorbent resin composition of an aminoacetic acid chelating agent and a water absorbent resin
  • Patent Literature 6 a water absorbent resin composition of an aminoacetic acid chelating agent and a water absorbent resin
  • Patent Literature 7 discloses an absorbent article containing manufactured tea and a water absorbent resin (Patent Literature 7) and a disposable diaper containing a water absorbent resin containing benzalkonium chloride and/or chlorhexidine gluconate (Patent Literature 8).
  • the patent literatures disclose a gelatinous insecticide prepared by causing a water absorbent resin to absorb a volatile monoterpene compound (Patent Literature 9), a method for producing a water absorbent resin composition in which an antibacterial membrane is formed on a surface of a water absorbent resin (Patent Literature 10), a water absorbent resin composition containing antibacterial phosphate (Patent Literatures 11 and 12), a water absorbent agent composition containing tannic acid (salt) and complex silicate compound (Patent Literature 13), a water absorbent agent composition containing a natural antibacterial ingredient extracted from grapefruit seeds and/or herbs (Patent Literature 14), a particulate water absorbent agent composition containing plant powder whose deodorizing index is not less than 180 (Patent Literature 15), a water absorbent agent composition obtained by covalent-bonding and/
  • Patent Literature 30 a water absorbent resin containing at least one substance selected from cyclodextrin having a fragrant material, dextrin derivative, C6-C10 unsaturated aliphatic aldehyde, and C6-C10 unsaturated aliphatic alcohol and a polycarboxylic acid water absorbent resin.
  • Patent Literature 31 a water absorbent resin whose L value in a Lab color system is not more than 90.
  • water absorbent resins containing compounds each of which gives an additional function such as a deodorant, an antibacterial agent, an aromatic agent, a coloring preventing agent, and a deterioration inhibitor.
  • the water absorbent resins using natural ingredients as disclosed in Patent Literatures 1, 2, 4, 7, 13-15, 21-24, 29 etc. are preferably used due to their high safeness.
  • qualities thereof are exactly managed, and only water absorbent resins whose physical properties (water absorbent performance and the aforementioned additional function) satisfy predetermined standards (so-called acceptable products) are sold.
  • the inventors of the present invention have found that a water absorbent resin which contains a natural ingredient and to which an additional function, a deodorizing function in particular, is given decreases the additional function with time after the water absorbent resin is sold with its targeted quality satisfied. That is, the inventors of the present invention have found that since the additional function decreases with time after the water absorbent resin is produced, a period during which the water absorbent resin can be stored or stocked, i.e. a period during which a quality of the additional function given to the water absorbent resin is assured becomes shorter. Furthermore, the inventors of the present invention have found a problem such that in actual use of the water absorbent resin, the additional function cannot be carried out sufficiently.
  • EP 2 208 756 A1 discloses in a first aspect a water absorbent resin composition containing a water absorbent resin containing a polyacrylic acid (salt)-based water absorbent resin as a main component, and an extract of bamboo and an extract of tea; and in a second aspect a water absorbent resin containing a polyacrylic acid (salt)-based water absorbent resin as a main component, and at least two kinds of compounds selected from a group consisting of hexanoic acid (salt), ethyl butyrate, and 3-methyl-2-cyclopenten-1-one; as well as a method for producing said water absorbent resin compositions.
  • US 2004/0048955 A1 discloses a water-absorbent composition including a specific plant extract; a water-absorbent resin whose surface portion and/or periphery thereof is treated; and/or a water-absorbent resin having a specific property, preferably a water-absorbent resin having the following three characteristics: (1) a specific neutralization rate, (2) a specific particle diameter, and (3) a specific plant extract.
  • WO 2011/136238 A1 discloses a polyacrylate (salt) and a polyacrylate (salt) water-absorbent resin containing a tracer which can be verified back to the manufacturing process of the water-absorbent resin when dealing with various problems with the water-absorbent resin which can occur from the manufacturing process of the water-resistant resin, during the use thereof by a consumer, up until the disposal thereof.
  • the polyacrylate (salt) and the polyacrylate (salt) water-absorbent resin disclosed in WO 2011/136238 A1 have a carbon stable isotope ratio ( ⁇ 13 C) of at least -20 ⁇ when measured by accelerator mass spectrometry.
  • the inventors of the present invention have found a problem such that although basic water absorbent properties (water absorption capacity/water absorption capacity under load/permeability etc.) other than color hue of a water absorbent resin are approximately constant after being stored for a long term of several months to several years, the water absorbent resin decreases its additional function with time, and particularly a water absorbent resin to which an additional function (particularly deodorizing function) is given by using a natural ingredient decreases the additional function with time.
  • the inventors of the present invention conducted a diligent study so as to attain the object, and finally found that in the case of a conventional water absorbent resin having an additional function (a deodorizing function in particular), the additional function was decreased over time by combining the water absorbent resin with a natural ingredient (natural deodorizing ingredient in particular) which was frequently used to provide the additional function, and particularly that the combination of the natural ingredient with the water absorbent resin more rapidly decreased the additional function than use of the natural ingredient alone. From this finding, the inventors of the present invention found that the object was attained by adding a small amount of a temporal deterioration preventing agent to the water absorbent resin containing the natural ingredient, which was combined with the water absorbent resin.
  • a water absorbent agent composition in accordance with the present invention comprises: a polycarboxylic acid (salt)-based water absorbent resin as a main component; a natural ingredient; and a temporal deterioration preventing agent, wherein said water absorbent agent composition contains iron (Fe) in an amount of not more than 2 ppm, and wherein the temporal deterioration preventing agent is at least one kind of a compound selected from: water-soluble reducing agents selected from erythorbic acid, L-ascorbic acid, and sulfites; water-soluble oxidants selected from hypochlorous acids; phenylphenols; benzoic acid or esters thereof; and hydroxybenzoic acid or esters thereof, and wherein the natural ingredient is an extract of a plant selected from the group consisting of Theaceae and Fagaceae.
  • the temporal deterioration preventing agent is at least one kind of a compound selected from: water-soluble reducing agents selected from erythorbic acid, L-as
  • a method in accordance with the present invention for producing a water absorbent agent composition includes: simultaneously or separately mixing a natural ingredient and a temporal deterioration preventing agent with a water absorbent resin which is a crosslinked polymer of unsaturated monomers having carboxylic acid and/or a salt thereof, wherein said water absorbent agent composition contains iron (Fe) in an amount of not more than 2 ppm, and wherein the temporal deterioration preventing agent is at least one kind of a compound selected from: water-soluble reducing agents selected from erythorbic acid, L-ascorbic acid, and sulfites; water-soluble oxidants selected from hypochlorous acids; phenylphenols; benzoic acid or esters thereof; and hydroxybenzoic acid or esters thereof, and wherein the natural ingredient is an extract of a plant selected from the group consisting of Theaceae and Fagaceae.
  • a water absorbent agent composition in accordance with the present invention is obtainable by a method mentioned above for producing a water absorbent agent composition.
  • a water absorbent agent package in accordance with the present invention includes a sealed container filled with a water absorbent agent composition mentioned above.
  • a water absorbent agent composition storing or stocking method in accordance with the present invention includes storing a water absorbent agent package mentioned above in a packaged state for not less than 30 days until the water absorbent agent package is actually used.
  • a packaged absorbent article for urine absorption in accordance with the present invention contains a water absorbent agent composition mentioned above.
  • an absorbent article production method in accordance with the present invention includes producing an absorbent article for urine absorption by using a water absorbent agent composition containing: a packaged water absorbent resin as a main component; and a natural ingredient, the water absorbent agent composition further containing a temporal deterioration preventing agent, wherein said water absorbent agent composition contains iron (Fe) in an amount of not more than 2 ppm and wherein the temporal deterioration preventing agent is at least one kind of a compound selected from: water-soluble reducing agents selected from erythorbic acid, L-ascorbic acid, and sulfites; water-soluble oxidants selected from hypochlorous acids; phenylphenols; benzoic acid or esters thereof; and hydroxybenzoic acid or esters thereof, and wherein the natural ingredient is an extract of a plant selected from the group consisting of Theaceae and Fagaceae.
  • a water absorbent agent composition in accordance with the present invention is defined in claim 1.
  • An absorbent core of the present invention contains the water absorbent agent composition in accordance with claim 1 of the present invention, and is preferably used as, for example, an absorbing layer of an absorbent article such as a sanitary material.
  • an absorbent article in accordance with the present invention includes an absorbent core (absorbing layer) containing the water absorbent agent composition, a top sheet having liquid permeability, and a back sheet having liquid impermeability.
  • the water absorbent agent composition in accordance with the present invention allows an absorbent article to have an additional function (a deodorizing function in particular).
  • the water absorbent agent composition is a novel water absorbent agent composition which continues to have an excellent additional function (a deodorizing function in particular) even after being stored for a long term.
  • An absorbent core and an absorbent article of the present invention each contain the water absorbent agent composition so as to have an excellent additional function (a deodorizing function in particular) of the water absorbent agent composition. Therefore, the absorbent core and the absorbent article are each particularly preferably used for sanitary materials such as a paper diaper, a sanitary napkin, an adult incontinence pad, and an adult paper diaper.
  • a water absorbent agent composition in accordance with the present invention which water absorbent agent composition, when used (incorporated) in an absorbent article such as a paper diaper, is highly safe, has an excellent additional function (a deodorizing effect in particular), and can have the excellent additional function (the deodorizing effect in particular) even after being stored for a long term; a method for producing the water absorbent agent composition in accordance with the present invention; and an absorbent core and an absorbent article each containing the water absorbent agent composition in accordance with the present invention (each made of the water absorbent agent composition).
  • a “water absorbent resin” as used in the present invention means a water-swelling, water-insoluble gelatinizer in the form of a polymer. It should be noted here that the "water-swelling” means that a CRC (water absorption capacity without load) specified in ERT 441.2-02 is not less than 5 [g/g], and the “water-insoluble” means that an Ext (water soluble component) specified in ERT 470.2-02 is not more than 50 wt%.
  • the water absorbent resin can be designed as appropriate depending on its use, and therefore is not particularly limited in its design.
  • the water absorbent resin is preferably a hydrophilic crosslinked polymer obtained by polymerizing crosslinking unsaturated monomers each having a carboxyl group.
  • the water absorbent resin may be a water absorbent resin composition containing an additive (e.g. surfactant) etc., provided that the foregoing CRC and Ext are satisfied.
  • the water absorbent resin may be surface-crosslinked one or non-surface-crosslinked one, and is not particularly limited in its shape, and may be sheet-like, fiber-like, powder-like, film-like, gelatinous or the like.
  • a water absorbent resin having not yet been surface-crosslinked is referred to as a "water absorbent resin powder”
  • a water absorbent resin which has been surface-crosslinked is referred to as "water absorbent resin particles”.
  • polyacrylic acid (salt) means a polymer that optionally has a graft component and contains, as main components, repeating units constituted by an acrylic acid and/or a salt thereof (hereinafter referred to as acrylic acid (salt)).
  • acrylic acid (salt) as used in the present invention means a polymer that contains, as monomers other than a crosslinking agent, acrylic acids (salts) in an amount between 30 mol% and 100 mol%.
  • Water absorbent agent composition indicates a water absorbent resin composition whose main component is the aforementioned water absorbent resin and which contains a natural ingredient capable of giving an additional function below and a temporal deterioration preventing agent.
  • the water absorbent resin is preferably surface-crosslinked water absorbent resin particles.
  • "Main component” as used herein indicates that the water absorbent resin or the water absorbent resin particles (solid content) is contained in a range preferably of not less than 50 wt% and less than 100 wt%, more preferably of 60 to 99.9 wt%, still more preferably of 70 to 99 wt%, and particularly preferably of 80 to 98.9 wt% relative to the water absorbent agent composition.
  • EDANA European Disposables and Nonwovens Associations.
  • ERT EDANA Recommended Test Methods, which is the European-standard (actually, the world-standard) method of measuring water absorbent resins.
  • the ERT is a method for measuring physical properties of a water absorbent resin
  • the measurements of physical properties of the water absorbent agent composition are carried out in conformity with the original ERT (known document: revised in 2002). In the following description, physical properties of the water absorbent agent composition are described.
  • CRC stands for a centrifuge retention capacity, and means water absorption capacity without load (hereinafter may be referred to as “water absorption capacity”).
  • water absorption capacity water absorption capacity
  • the “CRC” is water absorption capacity (Unit: [g/g]) observed in 0.2 g of a water absorbent agent composition in an unwoven cloth when the water absorbent agent composition is allowed to freely swell in an excess amount of 0.9 wt% aqueous solution of sodium chloride without load for 30min and thereafter is subjected to water spinning-off with use of a centrifugal machine.
  • AAP stands for absorption against pressure, and means water absorption capacity under load. Specifically, the “AAP” is water absorption capacity (Unit: [g/g]) observed in 0.9 g of a water absorbent agent composition after the water absorbent agent composition is allowed to swell in an excess amount of a 0.9 wt% aqueous solution of sodium chloride under a load of 2.06 kPa (0.3 psi) for 1 hour.
  • Ext stands for Extractables, and means a water soluble component (the amount of extractable components). Specifically, the “Ext” is a value (Unit: wt%) measured by pH titration to measure the amount of polymers dissolved in a solution obtained by adding 1.0 g of a water absorbent agent composition to 200 ml of a 0.9 wt% aqueous solution of sodium chloride and stirring the solution with a stir bar of 30 mm in length at 500 rpm for 16 hours.
  • residual monomers means an amount of monomers remaining in a water absorbent agent composition.
  • residual monomers means a value (Unit: ppm) obtained by high-performance liquid chromatography to measure the amount of residual monomers dissolved in a solution prepared by adding 0.5 g of a water absorbent agent composition to 200 ml of a 0.9 wt% aqueous solution of sodium chloride and stirring the solution with a stir bar of 30 mm in length at 500 rpm for 2 hours.
  • PSD particle size distribution
  • D50 weight average particle diameter
  • ⁇ width thereof
  • SFC Saline Flow Conductivity
  • GFP Gel Bed Permeability
  • SFC Seline Flow Conductivity
  • the phrase "X to Y”, which is indicative of a range, means that "not less than X but not more than Y".
  • the term “t (ton)”, which is a unit of weight, means a “metric ton”.
  • the term “ppm” means “ppm by weight” or “ppm by mass”.
  • weight and “mass” are treated as being synonymous
  • “part by weight” and “part by mass” are treated as being synonymous.
  • “acid (salt)” means “acid and/or salt thereof”
  • the term “meth(acryl)” means “acryl and/or methacryl”.
  • the following description discusses a method for producing a water absorbent resin, preferably water absorbent resin particles for use as a main component of the water absorbent agent composition in accordance with the present invention.
  • a polymerization step of the present invention is a step of obtaining a hydrous gelatinous crosslinking polymer (hereinafter referred to as a "hydrogel”) by polymerizing acid radical-containing unsaturated monomers.
  • a hydrous gelatinous crosslinking polymer hereinafter referred to as a "hydrogel”
  • a water absorbent resin which has a crosslinked structure and is obtained by polymerizing acid radical-containing unsaturated monomers is essentially used in an embodiment of the present invention.
  • an acid radical-containing unsaturated monomer for use in the present invention include monomers (such as acrylonitrile) which become an acid radical by a hydrolysis after polymerization.
  • a monomer which has an acid radical at polymerization is preferably used, and an unsaturated monomer which has carboxylic acid and/or a salt thereof is more preferably used.
  • a water absorbent resin which is obtained by polymerizing the acid radical-containing monomers include (partially) neutralized crosslinked polycarboxylic acid (salt) such as (partially) neutralized crosslinked polyacrylic acid, a hydrolyzed starch-acrylonitrile graft polymer, a neutralized starch-acrylic acid graft polymer, a saponified vinyl acetate-acrylic acid ester copolymer, crosslinked carboxymethylcellulose, a hydrolyzed acrylonitrile copolymer or acrylamide copolymer, or a crosslinked hydrolyzed acrylonitrile copolymer or acrylamide copolymer, a crosslinked cationic monomer, a carboxyl group-containing crosslinked polyvinyl denatured alcohol, a crosslinked isobutylene-maleic anhydride copolymer, and crosslinked 2-acrylamide-2-methylpropanesulfonic acid and acrylic acid, etc.
  • salt such as (partially) neutralized crosslinked
  • a polycarboxylic acid (salt)-based water absorbent resin particularly (partially) neutralized crosslinked polyacrylic acid (also referred to as a "polyacrylic acid (salt)-based water absorbent resin" obtained by polymerizing monomers having acrylic acid and/or a salt thereof (neutralized product) as a main component is more preferable.
  • an acid radical has a neutralization rate (mol% of a neutralized acid radical relative to the total acid radical in a case where an acid radical contained in a water absorbent resin is 100 mol%) preferably of 10 to 100 mol%, more preferably of 20 to 90 mol%, still more preferably of 30 to 80 mol%, and particularly preferably of 40 to 80 mol%.
  • the acid radical-containing unsaturated monomers each containing acrylic acid (salt) as a main component
  • the acid radical-containing unsaturated monomers can each optionally contain a graft polymer component (e.g., water absorbent resin fine powder, polyvinyl alcohol, starch, cellulose, or the like) in an amount of 0 to 30 wt% relative to the acrylic acid (salt) as a main component.
  • a graft polymer component e.g., water absorbent resin fine powder, polyvinyl alcohol, starch, cellulose, or the like
  • the other monomers to be used in combination include water-soluble or hydrophobic unsaturated monomers such as methacrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, vinylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acryloxyalkane sulfonic acid and alkali metal salt or ammonium salt thereof, N-vinyl-2-pyrrolidone, N-vinylacetamide, (meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, isobutylene, and lauryl (meth)acrylate, and monomer compositions containing these monomers (copolymerization ingredients).
  • water-soluble or hydrophobic unsaturated monomers such
  • a ratio of the other monomers to the acid radical-containing unsaturated monomers be 0 to 30 mol% relative to acrylic acid (salt) contained in the acid radical-containing unsaturated monomers as a main component (a ratio of the acrylic acid (salt) to the acid radical-containing unsaturated monomers be approximately not less than 77 mol%). It is more preferable that a ratio of the other monomers to the acid radical-containing unsaturated monomers be 0 to 10 mol% relative to acrylic acid (salt) contained in the acid radical-containing unsaturated monomers as a main component (a ratio of the acrylic acid (salt) to the acid radical-containing unsaturated monomers be approximately not less than 91 mol%).
  • a crosslinked structure is essential to a water absorbent resin to be used.
  • the crosslinked structure may be a self-crosslinking-type structure which is obtained by using no crosslinking agent; or a structure which is obtained by carrying out crosslinking by using a crosslinking agent (internal crosslinking agent) having, in one molecule, two or more polymerizable unsaturated groups or reactive groups, and is preferably a crosslinked structure which is obtained by carrying out crosslinking (copolymerization or a reaction) by using the internal crosslinking agent.
  • a crosslinking agent internal crosslinking agent
  • the internal crosslinking agent examples include N,N'-methylenebis(meth)acrylamide, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerine tri(meth)acrylate, glycerine acrylate methacrylate, ethylene oxide denatured trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, poly(meth)allyloxyalkane, (poly)ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene glycol, propy
  • These internal crosslinking agents may be appropriately used alone or in combination of two or more kinds. From the viewpoint of, for example, a water absorbent property of a water absorbent agent composition to be finally obtained, it is preferable to use a crosslinking agent which contains two or more polymerizable unsaturated groups. Further, the internal crosslinking agent is used in an amount preferably of 0.001 to 2 mol%, more preferably of 0.005 to 0.5 mol%, still more preferably of 0.01 to 0.2 mol%, and particularly preferably of 0.03 to 0.15 mol%, relative to the acid radical-containing unsaturated monomers (excluding the crosslinking agent).
  • the water absorbent resin of the present invention In a case where the internal crosslinking agent is used in an amount falling within the above range, it is possible to provide the water absorbent resin of the present invention with a sufficient water absorbent property.
  • a degradable soluble component (described later) is reduced (to, for example, not more than 40%) by, for example, increasing the internal crosslinking agent in amount (to, for example, 0.1 mol%).
  • the degradable soluble component may be reduced by using a water-soluble chain transfer agent at polymerization.
  • a polymerization initiator for use in an embodiment of the present invention is appropriately selected in accordance with a form of polymerization. Therefore, such a polymerization initiator is not particularly limited.
  • the polymerization initiator is exemplified by a photolytic polymerization initiator, a pyrolytic polymerization initiator, a redox polymerization initiator, and the like. From the viewpoint of a physical property (e.g., a water absorbent property), the polymerization initiator is used in an amount preferably of 0.0001 to 2 mol%, and more preferably of 0.01 to 0.1 mol%, relative to the acid radical-containing unsaturated monomers.
  • the polymerization initiator is used in an amount falling within the above range, it is possible to reduce residual monomers while maintaining, at a high level, a water absorbent property of the water absorbent resin of the present invention as a water-swelling or water-insoluble polymer gelatinizer.
  • examples of the photolytic polymerization initiator include a benzoin derivative, a benzyl derivative, an acetophenone derivative, a benzophenone derivative, an azo compound, and the like.
  • examples of the pyrolytic polymerization initiator include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; peroxides such as hydrogen peroxide, t-butyl peroxide, and methylethylketone peroxide; azo compounds such as 2,2'-azobis(2-amidino propane)dihydrochloride and 2,2'-azobis[2-(2-imidazoine-2-yl)propane]dihydrochloride; and the like.
  • the redox polymerization initiator is exemplified by a combination of a persulfate or a peroxide described above and a reducing compound such as L-ascorbic acid or sodium hydrogen sulfite.
  • a persulfate or a peroxide described above a reducing compound such as L-ascorbic acid or sodium hydrogen sulfite.
  • a reducing compound such as L-ascorbic acid or sodium hydrogen sulfite.
  • Use in combination of the photolytic polymerization initiator and the pyrolytic polymerization initiator may also be a preferable aspect of the present invention.
  • the water absorbent resin of the present invention can be obtained by carrying out bulk polymerization or precipitation polymerization of the acid radical-containing unsaturated monomers (hereinafter merely referred to as "monomers"). From the viewpoint of a water absorbent property, easiness of control of polymerization, and the like, it is preferable to carry out spray polymerization, drop polymerization, aqueous solution polymerization, or reverse phase suspension polymerization in which the monomers are in a form of an aqueous solution (hereinafter referred to as a "monomeric aqueous solution"). Of these polymerization methods, from the viewpoint of stability and productivity during production, and a water absorbent property (a water absorption capacity/a water absorption capacity under load), aqueous solution polymerization or reverse phase suspension polymerization is particularly preferable.
  • aqueous solution polymerization or reverse phase suspension polymerization is particularly preferable.
  • a concentration (contained amount) of the monomers depends on a temperature of the monomeric aqueous solution or kinds of the monomers. Therefore, the concentration is not particularly limited.
  • the monomeric aqueous solution contains the monomers in an amount preferably of 10 to 70 wt%, and more preferably of 20 to 60 wt%.
  • the monomeric aqueous solution which contains the monomers in an amount falling within the above range allows an improvement in water absorbent property of the water absorbent resin of the present invention.
  • the water absorbent agent composition contains iron (Fe) in an amount of not more than 2 ppm (described later) by, for example, controlling an amount of Fe contained in a base for use in neutralization.
  • the acid radical-containing unsaturated monomers (per solid content) of the present invention contain iron (Fe) in an amount preferably of not more than 2 ppm, more preferably of not more than 1.5 ppm, still more preferably of not more than 1 ppm, and particularly preferably of not more than 0.5 ppm.
  • Fe iron
  • a lower limit of the amount of Fe is preferably 0.001 ppm, and more preferably 0.01 ppm.
  • the aqueous solution polymerization is a method in which a monomer aqueous solution is polymerized without using any dispersion solvent.
  • the aqueous solution polymerization method is disclosed in U.S. Patents such as U.S. Patent No. 4625001 , U.S. Patent No. 4873299 , U.S. Patent No. 4286082 , U.S. Patent No. 4973632 , U.S. Patent No. 4985518 , U.S. Patent No. 5124416 , U.S. Patent No. 5250640 , U.S. Patent No. 5264495 , U.S. Patent No. 5145906 , and U.S. Patent No. 5380808 ; and European Patents such as European Patent No. 0811636 , European Patent No. 0955086 , and European Patent No. 0922717 .
  • the reverse phase suspension polymerization is a polymerization method in which a monomer aqueous solution is suspended in a hydrophobic organic solvent.
  • the reverse phase suspension polymerization is disclosed in U.S. Patents such as U.S. Patent No. 4093776 , U.S. Patent No. 4367323 , U.S. Patent No. 4446261 , U.S. Patent No. 4683274 , and U.S. Patent No. 5244735 .
  • monomers or polymerization initiators, methods for drying after polymerization, or the like described in the above U.S. Patents or European Patents are also applicable to an embodiment of the present invention.
  • Such polymerization as described above can also be carried out in an air atmosphere.
  • the polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon (e.g., at an oxygen concentration of not more than 1 vol%). It is preferable that the polymerization be carried out after dissolved oxygen contained in the monomers or the monomeric aqueous solution is sufficiently substituted with the inert gas (for example, the oxygen concentration becomes less than 1 [mg/l]).
  • a gel-crushing step of the present invention is a step of obtaining a particulate hydrogel by shredding, according to need, a hydrogel obtained in the polymerization step.
  • polymerization of the monomers and shredding of the hydrogel may be simultaneously carried out depending on a form of polymerization (e.g., kneader polymerization or the like).
  • the hydrogel obtained in the polymerization step may be dried as it is.
  • the hydrogel be shredded by use of, for example, a gel-crusher (a kneader, a meat chopper, or the like) during or after the polymerization according to need, and then be dried.
  • a gel-crusher a kneader, a meat chopper, or the like
  • the hydrogel is shredded by use of various methods, and how to shred the hydrogel is not particularly limited.
  • the hydrogel may be shredded by a method in which a screw-type extrusion machine that has a porous structure having any shape is used as a gel-crusher.
  • the particulate hydrogel has a weight average particle diameter preferably of 0.1 to 50 mm, more preferably of 0.2 to 10 mm, and still more preferably of 0.5 to 5 mm.
  • the particulate hydrogel which has a weight average particle diameter falling within the above range allows an improvement in water absorbent property of the water absorbent resin or the water absorbent agent composition of the present invention.
  • a drying step of the present invention is a step of obtaining a dried polymer by drying the particulate hydrogel (including the hydrogel).
  • a method for carrying out the drying is exemplified by but not particularly limited to heat drying, hot-air drying, reduced-pressure drying, infrared drying, microwave drying, drum dryer drying, dehydration by azeotropy with a hydrophobic organic solvent, high humidity drying by use of high-temperature water vapor, and the like.
  • hot-air drying or dehydration by azeotropy is preferable. Drying is carried out at a temperature falling within a range normally of 60 to 250°C, preferably of 100 to 220°C, and still more preferably of 120 to 200°C.
  • Drying time which depends on a surface area and/or a moisture content of the particulate hydrogel, a kind of a dryer, and the like, is appropriately set so that a water absorbent agent composition to be obtained has a moisture content falling within an intended range.
  • drying time is preferably 10 seconds to 2 hours, more preferably 1 minute to 1.5 hour, and still more preferably 10 minutes to 1 hour.
  • the particulate hydrogel discharged in the gel-crushing step is introduced into the drying step desirably in a shorter time, preferably within 2 hours, more preferably within 1 hour, still more preferably within 30 minutes, particularly preferably within 10 minutes, and most preferably within 2 minutes.
  • a pulverizing step of the present invention is a step of pulverizing, according to need, the dried polymer obtained in the drying step into particles having a size falling within a given range.
  • a method for carrying out the pulverization is exemplified by but not particularly limited to a method for carrying out the pulverization by use of, for example, a vibration mill, a roll granulator, a knuckle-type pulverizer, a high-speed rotation-type pulverizer (a pin mill, a hammer mill, a screw mill, a roll mill, or the like), a cylindrical mixer, or the like.
  • a classification step (first classification step) of the present invention is a step of obtaining water absorbent resin powder by sorting, into only particles having a given particle size, the dried polymer obtained after the drying step (and further pulverized in the pulverizing step according to need).
  • a method for carrying out the classification is exemplified by but not particularly limited to sieve classification by use of a sieve.
  • water absorbent resin powder to be obtained has a particle diameter of 150 to 850 ⁇ m
  • the dried polymer having passed through the mesh opening size of 850 ⁇ m is sieved by use of a sieve having a mesh opening size of 150 ⁇ m. This causes the dried polymer remaining on the sieve having a mesh opening size of 150 ⁇ m to be water absorbent resin powder having a particle diameter of 150 to 850 ⁇ m.
  • the water absorbent resin powder thus obtained which has a large surface area per unit weight, not only increases a water absorbent speed but also easily carries out an additional function (a deodorizing function in particular).
  • a shape of particles of the water absorbent resin powder is exemplified by but not particularly limited to, for example, a spherical shape, a crushed shape, or an indefinite shape. From the viewpoint of a size of a surface area, a non-uniformly pulverized shape is preferable.
  • the water absorbent resin powder has a bulk specific gravity (specified in JIS K-3362) preferably of 0.40 to 0.80 [g/ml], more preferably of 0.50 to 0.75 [g/ml], and still more preferably of 0.60 to 0.73 [g/ml].
  • the water absorbent resin powder has a moisture content (an amount of water contained in a water absorbent resin or a water absorbent agent composition; specified by a drying loss obtained when 1g of a water absorbent resin or a water absorbent agent composition is dried at 180 °C for 3 hours) preferably of 0.2 to 30 wt%, more preferably of 0.3 to 15 wt%, and still more preferably of 0.5 to 10 wt%.
  • a moisture content an amount of water contained in a water absorbent resin or a water absorbent agent composition; specified by a drying loss obtained when 1g of a water absorbent resin or a water absorbent agent composition is dried at 180 °C for 3 hours
  • a moisture content an amount of water contained in a water absorbent resin or a water absorbent agent composition; specified by a drying loss obtained when 1g of a water absorbent resin or a water absorbent agent composition is dried at 180 °C for 3 hours
  • the water absorbent resin powder is required to exhibit flowability at a normal temperature (20 to
  • the water absorbent resin powder which has a moisture content falling within the above range can have a higher impact resistance and maintain the additional function (the deodorizing function in particular) at a high level. Meanwhile, the water absorbent resin powder which has an excessively high moisture content causes not only a decrease in water absorbent performance but also accelerates decomposition of a natural ingredient, and may cause a temporal deterioration in additional function in some cases.
  • the water absorbent resin powder has a weight average particle diameter (D50) as a particle size preferably of 200 to 700 ⁇ m, more preferably of 300 to 600 ⁇ m, and still more preferably of 400 to 500 ⁇ m.
  • the water absorbent resin powder contains particles having a particle diameter of not less than 150 ⁇ m and less than 850 pm in a ratio preferably of not less than 90 wt%, more preferably of not less than 95 wt%, and still more preferably of not less than 98 wt% (upper limit: 100 wt%).
  • the water absorbent resin powder contains particles having a particle diameter of not less than 300 ⁇ m in a ratio preferably of not less than 60 wt%, more preferably of not less than 65 wt%, still more preferably of not less than 70 wt%, and particularly preferably of not less than 75 wt%.
  • the water absorbent resin powder which has a particle size falling within the above range allows an improvement in physical property (water absorption capacity under load and liquid permeability in particular) and further in moisture absorption blocking rate of the water absorbent resin of the present invention which water absorbent resin has been surface-crosslinked, so that a water absorbent resin composition which is suitable particularly to a sanitary material can be obtained.
  • the above particle size is applied to water absorbent resin particles which have been surface-crosslinked, and further to a water absorbent agent composition as an end product. Therefore, it is preferable to carry out a surface-crosslinking treatment with respect to water absorbent resin particles so that the water absorbent resin particles which have been surface-crosslinked continues to have a particle size falling within the above range. Further, the particle size may be adjusted after the surface-crosslinking according to need by, for example, crushing of an agglomerate after the surface-crosslinking (operation of breaking up an agglomerated particle), classification (a second classification step), or granulation.
  • a surface-crosslinking step of the present invention is a step of providing a part having a higher crosslink density for a surface layer of water absorbent resin powder to be obtained through the steps described earlier (a part of the water absorbent resin powder which part extends from a surface of the water absorbent resin powder to a place located at a depth of several ten ⁇ m from the surface).
  • the part having a higher crosslink density is formed by radical crosslinking or surface polymerization, a crosslinking reaction with a surface-crosslinking agent, or the like carried out on the surface of the water absorbent resin powder.
  • water absorbent resin powder to be obtained through the polymerization step, the drying step, the pulverizing step, and the classification step
  • water absorbent resin particles which have been surface-crosslinked allow an increase in absorption against pressure (AAP) and liquid permeability (e.g., SFC and GBP).
  • a water absorbent agent composition as a paper diaper not only improves in water absorbent performance but also improves in additional function (deodorizing function in particular) because a gap between particles of the water absorbent agent composition is maintained even after the water absorbent agent composition has been swollen.
  • a crosslinking agent (surface-crosslinking agent) for use in the surface-crosslinking step described earlier is exemplified by but not particularly limited to crosslinking agents mentioned in U.S. Patents such as U.S. Patent No. 5409771 , U.S. Patent No. 6228930 , U.S. Patent No. 6071976 , and U.S. Patent No. 6254990 .
  • crosslinking agent examples include polyhydric alcohol compounds such as mono, di, tri, tetra, or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3-pentanediol, polypropylene glycol, glycerine, polyglycerine, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,2-cyclohexanedimethanol; epoxy compounds such as ethylene glycol diglycidyl ether and glycidol; polyvalent amine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, and polyamide polyamine; haloepoxy compounds such as epich
  • one kind, or two or more kinds of the oxazolidinone compound(s), the alkylene carbonate compound(s), and the polyhydric alcohol compound(s) is/are preferably used.
  • a C2-C10 polyhydric alcohol compound is more preferably used, and a C3-C8 polyhydric alcohol compound is still more preferably used. It is particularly preferable that such a polyhydric alcohol compound and the other surface-crosslinking agent (preferably an oxazolidinone compound or an alkylene carbonate compound) be used in combination.
  • a used amount of the surface-crosslinking agent (in a case where a plurality of surface-crosslinking agents are used, a total amount of the plurality of surface-crosslinking agents) is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight, relative to 100 parts by weight of water absorbent resin powder, though depending on, for example, compounds to be used and a combination thereof.
  • the surface-crosslinking agent which is used in an amount falling within the above range allows a further improvement in water absorbent property of the water absorbent resin of the present invention.
  • water is used in an amount, preferably of 0.5 to 20 parts by weight, and more preferably of 0.5 to 10 parts by weight, relative to 100 parts by weight of the water absorbent resin powder.
  • a hydrophilic organic solvent is also usable. In this case, the hydrophilic organic solvent is used in an amount preferably of 0 to 5 parts by weight, and more preferably 0 to 3 parts by weight, relative to 100 parts by weight of the water absorbent resin powder.
  • a method in which the water or the hydrophilic organic solvent is added to or mixed with the water absorbent resin powder is not particularly limited.
  • the water, the hydrophilic organic solvent, or a mixture of the water and the hydrophilic organic solvent is prepared in advance and then mixed with the water absorbent resin powder preferably by spray or drop, more preferably by spray.
  • a liquid drop to be sprayed (the water, the hydrophilic organic solvent, or the mixture of the water and the hydrophilic organic solvent) has a size preferably of not more than 300 ⁇ m, and more preferably of not more than 200 ⁇ m.
  • the liquid drop which has a size falling within the above range allows a further improvement in physical property of the water absorbent resin of the present invention which water absorbent resin has been surface-crosslinked.
  • water-insoluble microparticles or a surfactant may coexist with the water or the hydrophilic organic solvent and the water absorbent resin powder which are being mixed, provided that the coexistence does not impair an effect of a water absorbent property of the water absorbent resin in accordance with the present invention.
  • the water absorbent resin powder to/with which the surface-crosslinking agent has been added/mixed is preferably subjected to a heat treatment.
  • a heat treatment is carried out, not only the surface-crosslinking agent reacts so as to adjust a water absorption capacity (CRC) and a water absorption capacity under load (AAP) of the water absorbent resin to fall within a preferable range (described later), but also an effect of preventing so-called gel blocking is obtained.
  • the heat treatment is carried out at a temperature (a temperature of a mixture of the water absorbent resin powder and the surface-crosslinking agent) preferably of 100 to 250 °C, and more preferably of 150 to 250 °C. Further, the heat treatment is carried out preferably for 1 minute to 2 hours. Note that a combination of a time and a temperature during the heat treatment is preferably 0.1 to 1.5 hour at 180 °C, and 0.1 to 1 hour at 200 °C.
  • water absorption capacity decreases preferably to 1 to 20 [g/g], and more preferably to 2 to 15 [g/g] in a period in which the surface-crosslinking step has not been carried out and then has been carried out
  • water absorbent resin particles which have been surface-crosslinked have a higher water absorption capacity under load (AAP).
  • the water absorbent resin which has been surface-crosslinked and a water absorbent agent composition to be obtained each has an AAP (specified in ERT442.2-02) preferably of not less than 15 [g/g], more preferably of 20 to 45 [g/g], still more preferably of 25 to 40 [g/g], and particularly preferably of 28 to 40 [g/g
  • AAP specified in ERT442.2-02
  • the water absorbent agent composition in accordance with the present invention is a composition which contains not only a water absorbent resin serving as a main component but also a natural ingredient as defined in claim 1 which allows the water absorbent agent composition to have an additional function, and a temporal deterioration preventing agent as defined in claim 1 which allows the water absorbent agent composition to continue to have the additional function even after the water absorbent agent composition is stored for a long term. Therefore, a case where no natural ingredient is used, or a case where only the temporal deterioration preventing agent is used may cause the additional function (the deodorizing function in particular) to be less effective, or cause a problem of safety and/or an odor and does not fall within the scope of the present invention.
  • the water absorbent agent composition contains the water absorbent resin (a solid content of the water absorbent resin) in a ratio preferably of not less than 50 wt% and less than 100 wt%, more preferably of 60 to 99.9 wt%, still more preferably of 70 to 99 wt%, and particularly preferably of 80 to 98.9 wt%.
  • the water absorbent resin contained in a ratio falling within the above range allows an improvement in water absorbent property of the water absorbent agent composition in accordance with the present invention.
  • the water absorbent resin to be used a main component is not particularly limited. However, according to the present invention, from the viewpoint of a water absorbent property, the water absorbent resin is preferably water absorbent resin particles which have been surface-crosslinked.
  • a “natural ingredient” in accordance with the present invention is an ingredient which is capable of adding, to a water absorbent resin, functions such as deodorizing, antibacterial, and aromatizing functions, particularly preferably the deodorizing function, and refers to an ingredient which is a plant-derived ingredient (plant ingredient), namely an extract of a plant selected from the group consisting of Theaceae and Fagaceae.
  • plant ingredient namely an extract of a plant selected from the group consisting of Theaceae and Fagaceae.
  • the natural ingredient in accordance with the present invention is capable of adding the deodorizing function.
  • the natural ingredient, which is an ingredient other than the water absorbent resin contains no raw ingredient (e.g., graft component or main chain) for use in a method for producing the water absorbent resin.
  • the natural ingredient may be in a form of a natural ingredient purified as a single-component compound.
  • the natural ingredient which may be in a form of a mixture, is exemplified by a natural product per se such as plant powder, essence (essential oil) extracted from a natural product, and plant sediment or essence sediment obtained as a by-product during a production process of a food-processing industry or a foodstuff-processing industry.
  • the natural ingredient may be in a form of a liquid or an aqueous solution at a normal temperature (20 to 25 °C, particularly 25 °C).
  • An ingredient which is a solid at a normal temperature may be mixed in a form of powder, but is more preferably mixed in a form of an aqueous solution to the water absorbent resin.
  • the natural ingredient of the present invention is a natural product per se such as the plant powder or an ingredient which is a solid at a normal temperature and has been extracted from a natural product, or essence (essential oil)-supported powder
  • a natural ingredient has a particle diameter normally of 0.001 to 1000 ⁇ m, and preferably of 1 to 600 ⁇ m.
  • such powder has a weight average particle diameter (D50) preferably of not more than 500 ⁇ m, and more preferably of not more than 300 ⁇ m.
  • the weight average particle diameter (D50) which exceeds 500 ⁇ m causes an action of an effective ingredient contained in the natural ingredient to be insufficient when a body fluid such as human urine is brought into contact with the water absorbent agent composition.
  • the natural ingredient-supported powder is preferably smaller in weight average particle diameter (D50) than the water absorbent resin since it is possible to more stably provide the water absorbent resin with the functions such as the deodorizing function.
  • a binder is also preferably added.
  • the binder is preferably water, polyhydric alcohol, C3-C6 polyol, polyethylene glycol, or the like. That is, a water absorbent agent in accordance with the present invention preferably contains polyol. Polyol is suitably contained in an amount falling within a range (described later).
  • a raw plant of the plant ingredient which is capable of adding the deodorizing function is exemplified by Theaceae and Fagaceae.
  • a plant belonging to Theaceae is exemplified by a camellia, a sasanqua, a tea plant, Eurya japonica, Ternstroemia japonica, and the like, and is more preferably exemplified by a tea plant.
  • a plant belonging to Fagaceae is exemplified by Fagus crenata , Quercus serrata, Quercus crispula, an oak, and the like, and is more preferably exemplified by an oak.
  • a plant-derived ingredient which is capable of adding the deodorizing function is exemplified by polyphenol, caffeine, and the like each contained in a plant, and is preferably exemplified by polyphenol, caffeine, and the like each contained in plants such as Theaceae and Fagaceae, and is particularly preferably exemplified by polyphenol contained in a plant.
  • polyphenol contained in the plant polyphenol containing flavonoid, phenylic acid, ellagic acid, lignan, curcumin, and coumalin is preferable, polyphenol containing flavonoid, ellagic acid, and lignan is more preferable, and polyphenol containing flavonoid is still more preferable.
  • the flavonoid preferably contains catechin, anthocyanin, tannin, rutin, and isoflavone, and more preferably contains catechin and tannin.
  • the catechin is preferably exemplified by tea catechin and a derivative thereof.
  • the tannin is exemplified by hydrolyzable tannin and condensed tannin, and condensed tannin is more preferable.
  • At least one kind, preferably two or more kinds, and more preferably three or kinds of plant ingredient(s) selected from polyphenol containing flavonoid such as catechin, tannin, and isoflavone; caffeine; and the like may be contained as a natural ingredient in an amount of more than 0 and not more than 100 wt%.
  • the plant ingredient be exemplified by at least one kind selected from tannin, tannic acid, a nutgall, a gallnut, and a gallic acid.
  • a molecular weight of polyphenol is appropriately selected, and the molecular weight is preferably 500 to 20000, and is more preferably 1000 to 10000.
  • the tannin is exemplified by hydrolyzable tannin and condensed tannin, and condensed tannin is more preferable.
  • the natural ingredient is used in an amount preferably of 0.00001 to 15 wt%, more preferably of 0.0001 to 10 wt%, still more preferably of 0.001 to 7 wt%, and particularly preferably of 0.01 to 6 wt%, relative to the solid content of the water absorbent resin.
  • the used amount of the natural ingredient is less than 0.00001 wt%, it may be impossible to provide a sufficient additional function.
  • the used amount of the natural ingredient is more than 15 wt%, it may be impossible to obtain an effect corresponding to the used amount.
  • the used amount of the natural ingredient is specified by a solid content excluding a solvent in a case where the natural ingredient is added in a form of a solution.
  • the used amount of the natural ingredient can also be determined by use of a total contained amount of caffeine and/or catechins, or a contained amount of tannin. In this case, it is only necessary that the used amount of the natural ingredient be determined so that the total contained amount of caffeine and/or catechins is preferably 0.5 ppm to 1 wt%, more preferably 10 ppm to 0.5 wt%, still more preferably 20 ppm to 0.1 wt%, and particularly preferably 50 ppm to 0.1 wt%, relative to the solid content of the water absorbent resin.
  • the total contained amount of caffeine and/or catechins is found by extracting the water absorbent agent composition by use of, for example, water, a physiological saline solution, or a water-alcohol mixed solvent, concentrating a resulting extract according to need, and then quantitatively analyzing the extract by liquid chromatography or the like.
  • the contained amount of tannin is found by extracting a water absorbent agent composition by use of, for example, water, a physiological saline solution, or a water-alcohol mixed solvent, concentrating/drying and solidifying a resulting extract according to need, and then quantitatively analyzing the extract by, for example, absorption photometry by use of a Folin reagent or the like.
  • any one of the used amount of the natural ingredient, the total contained amount of caffeine and/or catechins, and the contained amount of tannin be satisfied. It is more preferable that both the used amount of the natural ingredient and the total contained amount of caffeine and/or catechins, or the contained amount of tannin be satisfied.
  • a “temporal deterioration preventing agent" in accordance with the present invention refers to a compound which is added so as to maintain an additional function (prevent a deterioration) even after a water absorbent agent composition having the additional function (a deodorizing function in particular) is stored for a long term (not less than 30 days) until the water absorbent agent composition is actually used.
  • the temporal deterioration preventing agent is at least one kind of a compound as defined in claim 1.
  • the temporal deterioration preventing agent is used in an amount preferably of 0.05 to 120 ppm, and more preferably of 0.1 to 100 ppm, relative to the solid content of the water absorbent resin. In a case where the used amount of the temporal deterioration preventing agent is less than 0.1 ppm, it may be impossible to provide the water absorbent resin of the present invention with a sufficient deterioration preventing effect.
  • the used amount of the temporal deterioration preventing agent is more than 100 ppm
  • the water absorbent agent composition is used as an absorbent article such as a paper diaper, more stress is placed on dermis (skin), so that problems of skin roughness, diaper rash, and the like may occur.
  • the used amount of the temporal deterioration preventing agent is specified by a solid content excluding a solvent such as a hydrophilic solvent in a case where the temporal deterioration preventing agent is added in a form of a solution.
  • an optimum used amount of the temporal deterioration preventing agent varies depending on a combination of the natural ingredient to be used and the temporal deterioration preventing agent to be used. Specifically, it is desirable to determine the used amount of the temporal deterioration preventing agent so that a rate of reduction in additional function which rate is specified by a percentage of an amount of reduction in natural ingredient when the natural ingredient is stored at a normal temperature (25 °C) for 30 days in a form of an aqueous solution (particularly a 1 wt% aqueous solution) is preferably not more than 50%, more preferably not more than 10%, and still more preferably not more than 1%.
  • a weight ratio of the temporal deterioration preventing agent to the natural ingredient (described earlier) is preferably 1/10000 to 1/10, more preferably 1/8000 to 1/50, and still more preferably 1/6000 to 1/100.
  • the weight ratio which is beyond the above range may make it impossible to obtain a sufficient deterioration preventing effect, may cause the temporal deterioration preventing agent which is in an excessive amount to be economically disadvantageous, and may cause a problem of, for example, skin roughness.
  • the temporal deterioration preventing agent is excessively used relative to the natural ingredient, some compounds (particularly a water-soluble oxidant, a water-soluble reducing agent, or the like) may cause a deterioration in water absorbent resin depending on a kind of the temporal deterioration preventing agent. Accordingly, it is preferable that the temporal deterioration preventing agent be used in a smaller amount than the natural ingredient.
  • the temporal deterioration preventing agent be powder or a liquid at a normal temperature (20 to 25 °C, particularly 25 °C). Furthermore, the temporal deterioration preventing agent can also be added, in a form of a solution containing a hydrophilic solvent, e.g., an aqueous solution, to the water absorbent resin. Moreover, in order that the additional function of the natural ingredient is maintained, it is more preferable that the temporal deterioration preventing agent be added to the water absorbent resin while being mixed with the natural ingredient.
  • the temporal deterioration preventing agent maintains or improves the additional function (the deodorizing function in particular) of the water absorbent agent composition and is at least one kind of a compound selected from: water-soluble reducing agents selected from erythorbic acid, L-ascorbic acid, and sulfites; water-soluble oxidants selected from hypochlorous acids; phenylphenols; benzoic acid or esters thereof; and hydroxybenzoic acid or esters thereof.
  • the temporal deterioration preventing agent is at least one kind of a compound selected from: water-soluble reducing agents selected from, erythorbic acid, L-ascorbic acid, and sulfites; water-soluble oxidants selected from hypochlorous acids as a preservative, phenylphenols (excluding methoxyphenols) such as ophenylphenol as a germicide and an antifungal agent; benzoic acid or esters thereof (preferably C1-C20 alkyl ester, and more preferably C1-C10 alkyl ester) as a germicide; and hydroxybenzoic acid or esters thereof (preferably C1-C20 alkyl ester, and more preferably C1-C10 alkyl ester) as a germicide.
  • the temporal deterioration preventing agent is preferably a benzoic acid or a benzoic acid ester, or a hydroxybenzoic acid or a hydroxybenzoic acid
  • benzoic acid ester examples include methylparaben (4-hydroxy-benzoic acid methyl), ethylparaben (4-hydroxy-benzoic acid ethyl), propylparaben (4-hydroxy-benzoic acid propyl), isopropylparaben (4-hydroxy-benzoic acid isopropyl), butylparaben (4-hydroxybenzoic acid butyl), isobutylparaben (4-hydroxy-benzoic acid isobutyl), benzilparaben (4-hydroxy-benzoic acid benzil), and the like, and paraben selected from these benzoic acid esters is preferably used.
  • the hydroxybenzoic acid is specifically exemplified by gallic acid
  • the hydroxybenzoic acid ester is specifically exemplified by propyl gallate.
  • temporal deterioration preventing agents at least one kind of a compound selected from: ascorbic acids such as L-ascorbic acid, sodium L-ascorbate, D-ascorbic acid, and sodium D-ascorbate; erythorbic acids such as erythorbic acid and sodium erythorbate; sorbic acids such as potassium sorbate and sodium sorbate; gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isoamyl gallate, octyl gallate, and lauryl gallate; and benzoic acids such as sodium benzoate, methylparaben (4-hydroxybenzoic acid methyl), ethylparaben (4-hydroxy-benzoic acid ethyl), propylparaben (4-hydroxy-benzoic acid propyl), isopropylparaben (4-hydroxy-benzoic acid isopropyl), butylparaben (4-hydroxy-benzoic acid
  • At least one kind of a compound selected from erythorbic acids, sorbic acids, and benzoic acids is still more preferable. At least one kind of a compound selected from benzoic acids is particularly preferable. In particular, a benzoic acid (salt) or an ester thereof, or a hydroxybenzoic acid (salt) or an ester thereof is more preferable, and a hydroxybenzoic acid ester is the most preferable.
  • a water absorbent agent composition in accordance with the present invention can be obtained by adding a natural ingredient and a deterioration preventing agent to water absorbent resin particles described in the above [2], and mixing the natural ingredient and the deterioration preventing agent with the water absorbent resin particles.
  • a method for producing the water absorbent agent composition is not particularly limited.
  • the method for producing the water absorbent agent composition is exemplified by a method in which a mixture of a natural ingredient and a temporal deterioration preventing agent is added to a water absorbent resin; a method in which a natural ingredient and a temporal deterioration preventing agent are separately added to a water absorbent resin; and the like.
  • the natural ingredient and/or the temporal deterioration preventing agent are/is a liquid material(s), specifically in a case where the natural ingredient and/or the temporal deterioration preventing agent are/is a liquid(s) at a normal temperature (20 to 25 °C, particularly 25 °C), or in a case where the natural ingredient and/or the temporal deterioration preventing agent are/is a solution(s) obtained by dissolving the natural ingredient and/or the temporal deterioration preventing agent in, for example, water, an aqueous solution, an organic solvent, or the like
  • the method for producing the water absorbent agent composition is exemplified by a method in which the natural ingredient and/or the temporal deterioration preventing agent are/is spray or drop-mixed with the water absorbent resin so that the natural ingredient and/or the temporal deterioration preventing agent are/is added to the water absorbent resin in a desired amount.
  • the method for producing the water absorbent agent composition is exemplified by a method in which the natural ingredient and/or the temporal deterioration preventing agent are/is directly mixed with the water absorbent resin so that the natural ingredient and/or the temporal deterioration preventing agent are/is added to the water absorbent resin in a desired amount (e.g., a dry blend method in the case of mixing of minute particles); a method in which, in order that the natural ingredient and/or the temporal deterioration preventing agent are/is added to the water absorbent resin in a desired amount, water, an aqueous solution, an organic solvent, or the like is spray or drop-mixed with the natural ingredient and/or the temporal deterioration preventing agent which have/has been directly mixed with the water absorbent resin; and the like.
  • the natural ingredient and the temporal deterioration preventing agent are preferably close to each other in the water absorbent resin so that a greater effect of the present invention is obtained. Therefore, it is preferable that the natural ingredient and the temporal deterioration preventing agent be added simultaneously, and it is more preferable that the natural ingredient and the temporal deterioration preventing agent be added in a form of a mixture.
  • a timing at which the natural ingredient and/or the temporal deterioration preventing agent are/is added is not particularly limited. It is possible to add the natural ingredient and/or the temporal deterioration preventing agent at each production step carried out during production of the water absorbent agent composition, or after the production step. Specifically, it is only necessary to add the natural ingredient and/or the temporal deterioration preventing agent preferably during a step carried out on and after the polymerization step, more preferably during a step carried out on and after the drying step, and still more preferably during a step carried out on and after the heat treatment in the surface-crosslinking step, during the production of the water absorbent resin.
  • the natural ingredient and/or the temporal deterioration preventing agent may be added to a hydrous gelatinous crosslinked polymer obtained at polymerization or after polymerization.
  • a step of the heat treatment in the surface-crosslinking is ended (e.g., during a cooling step).
  • the water absorbent resin has a temperature (powder temperature) preferably of 0 to 150 °C, more preferably of 40 to 100 °C, and still more preferably of 50 to 90 °C during the addition of the natural ingredient and/or the temporal deterioration preventing agent.
  • the water absorbent resin which has a temperature (powder temperature) falling within the above range makes it possible to prevent a decrease in additional function of the natural ingredient contained in the water absorbent agent composition in accordance with the present invention, and to prevent coloring of the water absorbent agent composition.
  • An optimum amount of water, water vapor, an aqueous solution containing water and a hydrophilic organic solvent, or the like which is added according to need during the addition of the natural ingredient and/or the temporal deterioration preventing agent varies in accordance with, for example, a kind and a particle size of the water absorbent resin.
  • water is added in an amount preferably of not more than 10 parts by weight, and more preferably of 1 to 5 parts by weight, relative to 100 parts by weight of a solid content of the water absorbent resin.
  • an aqueous solution containing water and a hydrophilic organic solvent is added in an amount preferably of not more than 10 parts by weight, and more preferably of 0.1 to 5 parts by weight, relative to 100 parts by weight of a solid content of the water absorbent resin.
  • the hydrophilic organic solvent is contained in the aqueous solution in an amount of 0 to 100 wt%, preferably in an amount of 1 to 50 wt%, and more preferably in an amount of 5 to 40 wt%.
  • a liquid temperature of an aqueous solution in a case where the natural ingredient and/or the temporal deterioration preventing agent are/is added in a form of a solution is appropriately determined.
  • the aqueous solution may be heated in view of its solubility and viscosity, and has a liquid temperature preferably of 0 to 100 °C, and more preferably of 20 to 50 °C.
  • the natural ingredient and/or the temporal deterioration preventing agent are/is added in a form of a mixture
  • the natural ingredient and/or the temporal deterioration preventing agent are/is preferably added in a form of a solution (an aqueous solution or a water dispersion) to the water absorbent resin
  • the natural ingredient contained in the aqueous solution or the water dispersion has a concentration of 0.1 to 80 wt%, and more preferably of 1 to 70 wt%.
  • Use of the hydrophilic organic solvent allows more uniform mixing. This makes it possible to reduce occurrence of a lump during mixing with the water absorbent resin and a load on (damage to) the water absorbent agent composition.
  • water accelerates spreading and fixation to the water absorbent resin.
  • the natural ingredient is added to the water absorbent resin by being diluted with, for example, a solvent, it is preferable that the natural ingredient be mixed with the water absorbent resin in minimal time (particularly within 24 hours) after being diluted at a concentration for being added.
  • hydrophilic organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, and t-butyl alcohol; ketones such as acetone and methylethylketone; ethers such as dioxane, alkoxy(poly)ethylene glycol, and tetrahydrofuran; amides such as ⁇ -caprolactam and N,N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerine, 2-butene-1,4-diol, 1,3-butanediol, 1,4-butanedi
  • the hydrophilic organic solvent is preferably an alcohol or polyhydric alcohol, more preferably a C2-C6 alcohol or polyhydric alcohol, still more preferably a C3-C5 alcohol or polyhydric alcohol, and particularly preferably a C3-C5 polyhydric alcohol.
  • the hydrophilic organic solvent is specifically exemplified preferably by ethyl alcohol, isopropyl alcohol, propylene glycol, and glycerine, and particularly preferably by ethyl alcohol and propylene glycol. That is, the water absorbent agent composition in accordance with the present invention preferably contains polyol.
  • the water absorbent agent composition which contains polyol is preferable since polyol allows maintenance of a water absorption capacity under load and a reduction in dust.
  • the mixed hydrophilic organic solvent, particularly polyol may be dried (removed) after mixing, react, or partially or entirely remain, a given amount of polyol is preferably contained in the water absorbent agent composition.
  • the hydrophilic organic solvent, particularly polyol is contained or used in an amount preferably of 0 to 10 parts by weight, more preferably of 0.001 to 5 parts by weight, and still more preferably of 0.01 to 1 part by weight, relative to 100 parts by weight of the water absorbent resin.
  • An amount of the hydrophilic organic solvent contained in the water absorbent agent composition can be appropriately controlled in accordance with a mixed amount (a heating temperature and time in a case where heating is carried out after mixing).
  • a polyhydric alcohol may be arranged such that a polyhydric alcohol derived from a reaction of alkylene carbonate, e.g., ethylene glycol derived from ethylene carbonate, or propylene glycol derived from propylene carbonate remains on a surface of the water absorbent resin.
  • alkylene carbonate e.g., ethylene glycol derived from ethylene carbonate, or propylene glycol derived from propylene carbonate
  • a chelating agent and a surfactant may be simultaneously or separately mixed.
  • a mixing apparatus which is used to add the natural ingredient and/or the temporal deterioration preventing agent to the water absorbent resin is exemplified by but not particularly limited to a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a V-shaped mixer, a ribbon mixer, a dual-arm kneader, a flow mixer, an air mixer, a rotating disc mixer, a roll mixer, a tumbling mixer, and the like. Note that a speed at which the mixing apparatus rotates is not particularly required. The mixing apparatus may rotate at either a high speed or a low speed.
  • the additional function (the deodorizing function in particular) are more effectively carried out
  • it is desired in a process for producing the water absorbent resin and the water absorbent agent composition that at least one, more preferably two or more (particularly a combination of (b) and (a) or (c)), still more preferably three or more (particularly a combination of (a), (b), and (c)), particularly preferably all four of steps specified by the following (a) through (d) be satisfied.
  • the water absorbent agent composition in accordance with the present invention more preferably contains a chelating agent.
  • the chelating agent which may be either a polymerized compound or a non-polymerized compound, is preferably a non-polymerized compound, from the viewpoint of effect.
  • the chelating agent is preferably a polyvalent compound selected from amino-polyvalent carboxylic acid, organic polyvalent phosphoric acid, inorganic polyvalent phosphoric acid, and amino-polyvalent phosphoric acid.
  • the chelating agent has a molecular weight preferably of 100 to 5000, and more preferably of 200 to 1000. Use of a suitable chelating agent makes it possible to obtain the water absorbent agent composition which further has a coloring preventing function and a deterioration preventing function.
  • a polyvalent compound which is taken as an example of the chelating agent is a compound which contains, in one molecule, a plurality of functional groups, preferably 2 to 30 functional groups, more preferably 3 to 20 functional groups, and still more preferably 4 to 10 functional groups.
  • a chelating agent is preferably a water-soluble chelating agent.
  • the chelating agent is preferably a water-soluble chelating agent to be dissolved in 100 g of water (25 °C) in an amount of not less than 1 g, and still more preferably a water-soluble chelating agent to be dissolved in 100 g of water (25 °C) in an amount of not less than 10 g.
  • amino-polyvalent carboxylic acid examples include iminodiacetic acid, hydroxyethyl iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, triethylene tetramine hexaacetic acid, trans-1,2-diaminocyclohexane tetraacetic acid, N,N-bis(2-hydroxyethyl)glycine, diaminopropanol tetraacetic acid, ethylenediamine dipropionic acid, hydroxyethylenediamine triacetic acid, glycol ether diaminetetraacetic acid, diaminopropane tetraacetic acid, N,N'-bis(2-hydroxybenzil)ethylenediamine-N,N'-diacetic acid, 1,6-hexamethylendiamine-N,N,N',N'-tetraacetic acid
  • Examples of the organic polyvalent phosphoric acid include nitriloacetic acid-di(methylenephosphinic acid), nitrilodiacetic acid-(methylenephosphinic acid), nitriloacetic acid- ⁇ -propionic acid-methylenephosphonic acid, nitrilotris(methylenephosphonic acid), 1-hydroxyethylidenediphosphonic acid, and the like.
  • Examples of the inorganic polyvalent phosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, salts of these inorganic polyvalent phosphoric acids, and the like.
  • amino-polyvalent phosphoric acid examples include ethylenediamine-N,N'-di(methylenephosphinic acid), ethylenediaminetetra(methylenephosphinic acid), cyclohexanediaminetetra(methylenephosphonic acid), ethylenediamine-N, N'-diacetic acid-N,N'-di(methylenephosphonic acid), ethylenediamine-N,N'-di(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), polymethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), salts of these amino-polyvalent phosphoric acids, and the like.
  • the chelating agent be present on an inside or a surface of the water absorbent resin.
  • the chelating agent is added to the inside or the surface of the water absorbent agent composition by being appropriately mixed by, for example, being mixed with monomers which are being polymerized, being mixed with a hydrogel which has been obtained by the polymerization and has not been dried, or being mixed with water absorbent resin powder which is obtained after the drying.
  • the polymerization step or the addition of the chelating agent may cause the water absorbent resin to have a degradable soluble component of not more than 40 wt%.
  • the present invention preferably includes the chelating agent addition step, and it is more preferable in the present invention to mix the chelating agent during or after the polymerization.
  • the chelating agent is added preferably in an amount of 0 to 5 wt%, more preferably in an amount of 10 ppm to I wt%, still more preferably in an amount of 50 to 5000 ppm, and particularly preferably in an amount of 100 to 2000 ppm, relative to the water absorbent resin.
  • the degradable soluble component may be adjusted to not more than 40 wt% in the polymerization step by a method other than the addition of the chelating agent, e.g., by highly crosslinking the water absorbent resin during the polymerization (e.g., using a crosslinking agent in an amount of not less than 0.1 mol%), or by using a water-soluble chain transfer agent (e.g., using hypophosphite in an amount of 0.01 to 1 mol% relative to monomers).
  • a method of the addition of the chelating agent is more preferable from the viewpoint of a physical property.
  • the water absorbent agent composition in accordance with the present invention contains Fe in an amount of not more than 2 ppm from the viewpoint of not only deodorization but also prevention of a deterioration and coloring thereof.
  • Fe contained in the water absorbent agent composition Fe be derived mainly from a base used for neutralization and contained in an amount (as a weight of Fe contained in the water absorbent agent composition) of not more than 2 ppm, preferably of not more than 1.5 ppm, more preferably of 1 ppm, and particularly preferably of not more than 0.5 ppm.
  • a lower limit of an amount of Fe is preferably 0.001 ppm, and more preferably 0.01 ppm.
  • the amount of iron (Fe) is controlled mainly by controlling a base (particularly caustic soda) which is used for neutralization. Besides, the control of the amount of iron (Fe) is also carried out by, for example, controlling trace iron of raw materials (acrylic acid, a crosslinking agent, water, etc.), or by controlling material properties of a resin coating, a glass coating, stainless steel, and the like of various water absorbent resin producing apparatuses such as a polymerization apparatus and a monomer pipe, and a pipe. Note that amounts of iron contained in the base and the water absorbent agent composition can be determined quantitatively by an ICP emission spectrochemical analysis method described in JIS K1200-6, for example, and International Publication No. 2008/090961 can be referred to as a reference on a quantitative determination method.
  • the step of mixing water-insoluble microparticles is carried out, handleability of the water absorbent resin and the water absorbent agent composition as powder, particularly flowability of powder under moisture absorption is enhanced.
  • the water-insoluble microparticles used in this step is exemplified by but not particularly limited to metallic oxides such as silicon dioxide and titanic oxide; silicic acids and silicates such as natural zeolite and synthetic zeolite; and inorganic powder such as kaolin, talc, clay, and bentonite. Of these water-insoluble microparticles, silicon dioxide and silicic acids and silicates are preferable.
  • the water-insoluble microparticles have an average particle diameter (measured by a Coulter counter method) preferably of not more than 200 ⁇ m, more preferably of 0.001 to 100 ⁇ m, and still more preferably of 0.01 to 10 ⁇ m.
  • the water-insoluble microparticles are added in an amount preferably of 0.001 to 10 parts by weight, more preferably of 0.01 to 5 parts by weight, still more preferably of 0.01 to 3 parts by weight, and particularly preferably of 0.01 to 1 part by weight, relative to 100 parts by weight of the water absorbent agent composition or the water absorbent resin.
  • a water absorption capacity under load of the water absorbent agent composition or the water absorbent resin can be maintained at a comparatively high level while a moisture absorption blocking rate and permeability of the water absorbent agent composition or the water absorbent resin of the present invention are maintained at a high level, or a reduction in water absorption capacity under load (AAP) due to the water-insoluble microparticles can be prevented.
  • AAP water absorption capacity under load
  • a method for mixing the water-insoluble microparticles is exemplified by but not particularly limited to a dry blend method in which microparticles are mixed, a wet blending method in which the water-insoluble microparticles are dispersed in a solution containing the natural ingredient and a surface-crosslinking agent, or in water, and the like.
  • the dry blend method is more preferable from the viewpoint of a mixing efficiency.
  • the water absorbent agent composition in accordance with the present invention has, as a later-mentioned water absorbent agent, a water absorption capacity without load (CRC) preferably of 10-100 [g/g], more preferably of 20-80 [g/g], still more preferably of 25-45 [g/g], and particularly preferably of 30-40 [g/g].
  • a water absorption capacity without load (CRC) of the water absorbent agent composition of the present invention being within the above range is preferable since this range allows sanitary goods such as paper diapers including the water absorbent agent composition to be excellent in performance of absorbing and retaining a body fluid such as urine and reduce an amount of the water absorbent agent composition used therein.
  • the water absorbent agent composition in accordance with the present invention has, as the later-mentioned water absorbent agent, a water soluble component (Ext) preferably of not more than 50 wt%, more preferably of not more than 25 wt%, still more preferably of not more than 20 wt%, particularly preferably of not more than 15 wt%, and most preferably of not more than 10 wt%.
  • a water soluble component (Ext) of the water absorbent agent composition of the present invention being within the above range is preferable since this range allows a reduction in stickiness when the water absorbent agent composition is used in paper diapers etc.
  • the water absorbent agent composition in accordance with the present invention has, as the later-mentioned water absorbent agent, a moisture content preferably of 0.2-30 wt%, more preferably of 0.3-20 wt%, still more preferably of 1.0-15 wt%, particularly preferably of 1.5-10 wt%, and most preferably of 2.0-10 wt%.
  • the moisture content of the water absorbent agent composition of the present invention being within the above range is preferable since this range allows the water absorbent agent composition to carry out the additional function more effectively, and to show flowability at normal temperatures, so that the water absorbent agent composition becomes powder with excellent handleability and has improved productivity.
  • the results of evaluation in deodorizing tests A carried out at the start and the end, respectively, of a test on stability in maintaining a deodorizing effect of the water absorbent agent composition are each not more than 3.3, and a stabilization index is in a range of 90 to 100%.
  • the result of evaluation in the deodorizing test A being not less than 3.4 is not preferable since such a value indicates that the deodorizing effect is insufficient.
  • the stabilization index being within the above range is preferable since this range allows a reduction in variation in deodorizing function of a later-mentioned water absorbent core and/or absorbent article (such as paper diapers).
  • the water absorbent agent composition in accordance with the present invention has a degradable soluble component preferably of not more than 40 wt%, more preferably of not more than 30 wt%, and still more preferably of not more than 25 wt%.
  • the lower limit of the degradable soluble component is not less than 5 wt% in consideration of balance with other physical properties (water absorption capacity in particular).
  • the degradable soluble component being not less than 40 wt% is not preferable since such a value may raise problems such as a deterioration in gel, skin roughness, rash, a deterioration in ability to remove offensive odor due to a body fluid such as urine, when the water absorbent agent composition is used for the later-mentioned water absorbent core and/or absorbent article (such as paper diapers).
  • the "degradable soluble component” indicates a water soluble component in consideration of a deterioration in gel due to urine, and is measured with a physiological saline solution to which L-ascorbic acid which promotes deterioration in gel is added (specified in the item (7-3) below).
  • the water absorbent agent composition in accordance with the present invention has a moisture absorption blocking ratio (BR) of not more than 30 wt%, more preferably of not more than 10 wt%, still more preferably of not more than 5 wt%, and particularly preferably of not more than 2 wt%.
  • BR moisture absorption blocking ratio
  • the moisture absorption blocking ratio (BR) being more than 30 wt% is not preferable since such a value may raise problems such as a problem such that worsened flowability of powder at a high humidity worsens handleability of the water absorbent agent composition, resulting in agglomeration and clogging of a water absorbent core in a production plant when the water absorbent core is prepared, or resulting in agglomeration and clogging of the water absorbent agent composition in a carrier pipe; and a problem such that the water absorbent agent composition cannot be evenly mixed with hydrophilic fibers.
  • the water absorbent agent composition in accordance with the present invention satisfies at least one of the following physical properties (1) through (4), more preferably two or more (particularly a combination of (2) and (1) or (3)), still more preferably three or more (particularly a combination of (1), (2), and (3)), particularly preferably all four of the physical properties.
  • the present invention also provides a package of the water absorbent agent composition and a method for storing or stocking the water absorbent agent package.
  • the "water absorbent agent package” indicates various kinds of sealed containers such as a container bag, a paper bag, and a silo filled with the water absorbent agent composition.
  • the water absorbent agent package can be transported, stored, or stocked.
  • a unit of a filling amount of the water absorbent agent package is not particularly limited, but is preferably 1 kg to 100 t, more preferably 10 kg to 10 t, and still more preferably 20 kg to 2t.
  • the water absorbent agent composition containing the natural ingredient and the temporal deterioration preventing agent in the form of the water absorbent agent package, it is possible to stably store or stock the water absorbent agent composition in a packed state for a long time, preferably for not less than 30 days, more preferably for not less than 60 days, and still more preferably for not more than 100 days (upper limit is 1000 days or so), and to maintain an additional function of the water absorbent agent composition, until the water absorbent agent composition is actually used.
  • a “water absorbent core” of the present invention indicates a shaped matter whose main components are the water absorbent agent composition described in the item [3] and a fiber base material (also referred to as a fiber material). That is, the water absorbent core is a shaped matter made of materials having a water-absorbing ability, and is preferably a matter whose water absorbing materials are the water absorbent agent composition and the fiber base material and whose shape is retained by a binder, unwoven cloth etc. if necessary.
  • the water absorbent core indicates a water absorbent core containing: a particulate water absorbent agent composition whose main component is a water absorbent resin which has a crosslinked structure and is obtained by polymerizing acid radical-containing unsaturated monomers; and hydrophilic fiber which is a fiber basic material.
  • the water absorbent agent composition contains the aforementioned natural ingredient and the temporal deterioration preventing agent.
  • the present invention is not limited to this, and the absorbent article may be, for example, one obtained by adding a natural ingredient and a temporal deterioration preventing agent to a fiber base material such as hydrophilic fiber so that the fiber base material contains the natural ingredient and the temporal deterioration preventing agent.
  • the water absorbent core can be produced by forming the water absorbent agent composition and the hydrophilic fiber into a sheet shape, cylinder shape etc.
  • the water absorbent core can be produced by using the water absorbent resin, the natural ingredient, the temporal deterioration preventing agent, and the hydrophilic fiber.
  • the water absorbent core can be easily produced by blending the hydrophilic fiber, the water absorbent agent composition, and if necessary other fiber base material, an adhesive or etc., or causing the water absorbent agent composition to be sandwiched between fiber base materials such as hydrophilic fibers, or other method.
  • the water absorbent core of the present invention may be one obtained by causing the water absorbent agent composition to be sandwiched between fibers other than the hydrophilic fibers, such as tissue paper, or one obtained by solidifying the water absorbent agent composition with an adhesive etc.
  • a core concentration which is defined as a contained amount of the water absorbent agent composition relative to a total weight of the water absorbent agent composition and the hydrophilic fiber, may be 100 wt%.
  • the core concentration is less than 100 wt%, preferably 10-90 wt%, more preferably 20-90 wt%, and still more preferably 25-80 wt%.
  • the core concentration is less than 10 wt%, an amount of the water absorbent agent composition used is small, so that there is a possibility that a deodorizing function is not given sufficiently to the whole of a paper diaper.
  • the core concentration is more than 90 wt%, an amount of the hydrophilic fiber used is small, so that there is a possibility that an effect yielded by use of the hydrophilic fiber is not obtained sufficiently.
  • the present invention also provides an absorbent article for absorbing urine, which uses the aforementioned packaged water absorbent agent composition, a method for producing the absorbent article, and a method for storing or stocking the absorbent article.
  • “Absorbent article” of the present invention indicates an absorbent core which is intermediate consumer goods or end consumer goods for general consumers which use the absorbent core.
  • the absorbent article include paper diapers, sanitary napkins, incontinence pads, pet sheets, litter, and the like.
  • a preferable example of the absorbent article is an absorbent article for absorbing urine.
  • a particularly preferable example of the absorbent article is a paper diaper.
  • the absorbent article paper diaper, sanitary napkin, incontinence pad, pet sheet etc.
  • the absorbent core includes the absorbent core, a top sheet having liquid permeability, and a back sheet having liquid impermeability.
  • a method for producing the absorbent article in accordance with the present invention is not particularly limited.
  • the absorbent article may be produced in such a manner that an absorbent core prepared by blending the fiber base material and the water absorbent agent composition or causing the water absorbent agent composition to be sandwiched between the fiber base materials is further sandwiched between a liquid-permeable base material (top sheet) and a liquid-impermeable base material (back sheet), and providing the resultant with an elastic member, a diffusion layer, an adhesive tape etc. if necessary. Consequently, an absorbent article, particularly a paper diaper and a sanitary napkin, is produced.
  • the absorbent article thus produced is compressed and shaped so that a concentration of the absorbent core therein is 0.06-0.50 [g/cm 3 ], and a basic weight is 0.01-0.20 [g/cm 2 ].
  • the fiber base material is not particularly limited as long as it is hydrophilic fiber.
  • the fiber base material include pulverized wood pulp, cotton linter, crosslinked cellulose fiber, rayon, cotton, wool, acetate fiber, vinylon, and the like, which are preferably air-laid.
  • the absorbent article can be stably stored or stocked in a packaged state for a long time, preferably for not less than 30 days, more preferably for not less than 60 days, and still more preferably for not less than 100 days (upper limit is 1,000 days or so) until the absorbent article is actually used, and can maintain an additional function for such a long time.
  • the water absorbent agent composition in accordance with the present invention can add an additional function (deodorizing function in particular) to the absorbent article, and carries out an excellent additional function (deodorizing function in particular) and an excellent absorbent property for a long time (not less than 30 days) until the absorbent article is actually used.
  • Such an absorbent article is not particularly limited. Specific examples of such an absorbent article include sanitary materials such as paper diapers for adults, paper diapers for children, sanitary napkins, incontinence pads, and the like. In these applications, amounts of Re-Wet are small, resulting in strong feeling of dryness.
  • the absorbent article has a deodorizing function in particular, it is possible to greatly reduce a burden not only on a user who is wearing the absorbent article but also on persons who care the user (in case of paper diapers for adults). Furthermore, not only in use of a paper diaper but also in disposing of or storing a used paper diaper, offensive odor is less likely to be generated or increase. This makes it easy to dispose of the used paper diaper in homes and facilities, and reduces necessity of special equipment for disposal (e.g. airtight container, instant collection of garbage).
  • special equipment for disposal e.g. airtight container, instant collection of garbage.
  • 50 ml was sampled from a mixture of human urine collected from 10 adults, and was poured into a 120 ml polypropylene vessel having a lid (product name: Pack-Ace, manufactured by Teraoka Co., Ltd.; size: 58 mm in bore diameter x 54 mm in bottom diameter x 74 mm in height).
  • the human urine used was obtained within 2 hours from urination.
  • a water absorbent agent composition was added to the polypropylene vessel containing 50 ml of the human urine, so that the water absorbent agent composition absorbed the human urine to be 25-times-swollen gel. Then, the vessel was covered with the lid and kept at 37 °C.
  • the deodorizing property was evaluated by 20 adult monitors who were selected arbitrarily. Determination of the deodorizing property was made in such a manner that every monitor made an evaluation based on five scales including "1: no smell”, “2: hardly noticeable smell”, “3: noticeable but sufferable smell”, “4: sharp smell", and “5: overpowering smell", the "5" being an odor obtained when the test was made with only human urine without addition of the water absorbent agent composition, and the deodorizing property was determined based on an average of evaluations of all the monitors.
  • a test on stability in maintaining a deodorizing effect is a test to evaluate or expect a deodorizing ability of a water absorbent agent composition which is processed by a user to be a paper diaper etc. and then actually used by an end customer, compared to a deodorizing ability of the water absorbent agent composition immediately after production thereof (normally, at this point, quality control of physical properties, including a water absorbent property, of the water absorbent agent composition is made and only acceptable products are shipped).
  • a stabilization index was obtained by carrying out an acceleration test below so as to evaluate a decrease in deodorizing ability of the water absorbent agent composition after production thereof (it was separately confirmed that other physical properties, including a water absorbent property, were not substantially changed).
  • the acceleration test was carried out as follows.
  • a targeted water absorbent agent composition was subjected to the deodorizing test A mentioned in the item (7-1) right after production of the water absorbent agent composition (within 3 days, preferably within 1 day, after the production), and a result of evaluation was Xa.
  • the water absorbent agent composition and human urine used were in such amounts as to provide not less than 100 g of swollen gel.
  • a water absorbent agent composition which was the same as the water absorbent agent composition used in the deodorizing test A, i.e. 100 g of the water absorbent agent composition which was not swollen, was put in a 250 ml polyethylene vessel (reagent bottle manufactured by TOP; polypropylene wide-mouth bottle), and the polyethylene vessel was covered with a lid so as to be a water absorbent agent package. Then, the water absorbent agent package was left (stored) at a temperature of 40 °C for 30 days in an atmosphere of 75 %RH in relative humidity.
  • the water absorbent composition taken out from the water absorbent agent package left for 30 days was subjected to the deodorizing test A which used human urine collected from the same 10 adults as those in the former deodorizing test A (whose physical conditions and dietary lives were the same as those in the former deodorizing test A) and which was monitored by the same 20 adults as in the former deodorizing test A.
  • a result of the evaluation was Xb.
  • pH electrode to be used in measurement of a degradable soluble component was calibrated with pH standard buffers (pH: 4.0, pH: 7.0, pH: 10.0).
  • L-ascorbic acid was added to a physiological saline solution which had been prepared beforehand so that a concentration of the L-ascorbic acid was 0.05 wt%, and thus a deterioration test solution was prepared. That is, 0.5 g of L-ascorbic acid was dissolved in 999.5 g of a physiological saline solution so as to prepare a 1000.0 g of a deterioration test solution.
  • Wa [g] indicates a relative weight of a unit having an acid radical in the extractable contents of the water absorbent agent composition
  • Wb [g] indicates a relative weight of a unit having a carboxyl group (carboxylate) neutralized with a basic substance in the extractable contents of the water absorbent agent composition.
  • Wa [g] and Wb [g] can be obtained based on respective Equations (3) and (4) below.
  • Wa g Na ⁇ 72 ⁇ 200 / F
  • Equation (3) is a weight of a repeating unit per 1 mol of an acrylic acid polymer
  • Equation (4) is a weight of a repeating unit per 1 mol of a sodium acrylate.
  • monomers having an acid radical other than acrylic acid are copolymerized or in a case where alkaline metal salt other than sodium salt, such as potassium salt, lithium salt etc., are used, the above "72” or “94” is appropriately converted into an average weight of a repeating unit per 1 mol containing the monomer or the alkaline metal salt.
  • Na [mol] in the Equation (3) indicates an amount by mole of an acid radical in extractable contents in the titration liquid (filtrate).
  • Nb [mol] in the Equation (4) indicates an amount by mole of a carboxyl group (carboxylate) neutralized with a basic substance in the extractable contents in the titration liquid (filtrate).
  • Na [mol] and Nb [mol] can be obtained based on respective Equations (5) and (6) below.
  • Na mol Va ⁇ Vab / 1000 ⁇ 0.1
  • Nb mol N 1 ⁇ Na
  • N 1 [mol] in the Equation (6) is the whole amount by mole of extractable contents in the titration liquid (filtrate), and can be obtained based on Equation (7) below.
  • N 1 mol Vb ⁇ Vbb / 1000 ⁇ 0.1
  • a back sheet (liquid-impermeable sheet) having a so-called leg gather made of liquid-impermeable polypropylene, the aforementioned absorbent core, and a top sheet (liquid-permeable sheet) made of liquid-permeable polypropylene were attached to each other in this order with use of a double-faced tape.
  • two so-called tape zip fasteners were attached to the resultant, so that an absorbent article (i.e. paper diaper) was formed.
  • the weight of the absorbent article was 46 g.
  • the absorbent article prepared by the above operation was cut into pieces of 10 cm ⁇ 10 cm in size, and the pieces were put in a 250 ml polypropylene vessel having a lid (product name: Pack-Ace/manufactured by Teraoka Co., Ltd.; size: 58 mm in bore diameter ⁇ 54 mm in bottom diameter ⁇ 154 mm in height).
  • the lid was removed from the vessel, and odor was smelled at a position approximately 3 cm above the opening of the vessel, and a deodorizing property of the absorbent article was evaluated based on a standard below.
  • the deodorizing property was evaluated by 20 adult monitors who were selected arbitrarily. Determination of the deodorizing property was made based on a standard which was odor obtained when the same operation was made with only human urine poured into the vessel without use of the absorbent article. Every monitor made an evaluation based on six scales including "0: no smell”, “1: scarcely noticeable smell”, “2: noticeable but sufferable smell”, “3: easily noticeable smell”, “4: sharp smell", and “5: overpowering smell", the "5" being the standard odor, and the deodorizing property was determined based on an average of evaluations of all the monitors.
  • the water absorbent agent composition was added to 200 ml of a 0.9 wt% aqueous solution of sodium chloride, and the resultant was stirred for 2 hours at 500 rpm, so that an extract liquid was obtained.
  • the extract liquid was analyzed with a highperformance liquid chromatography, the height or the area of a peak of each ingredient was compared with the height or the area of a peak of a standard material, so that the contained amount of the ingredient was obtained.
  • the water absorbent agent composition contains an appropriate amount of the natural ingredient.
  • Determination of a natural ingredient (tannin) in the water absorbent agent composition was made by a Folin Ciocalteu method or a Folin Denis method.
  • the water absorbent agent composition was added to 200 ml of a 0.9 wt% aqueous solution of sodium chloride, and stirred at 500 rpm for 2 hours so as to obtain an extract liquid.
  • the extract liquid was mixed with a Folin reagent and the degree of coloring by reduction was measured by absorption spectroscopy, so that the contained amount of a natural ingredient (tannin) in the water absorbent agent composition was obtained.
  • the water absorbent agent composition in the aluminum cup was softly moved onto a JIS standard sieve of JIS 8.6 meshes (mesh opening size was 2,000 ⁇ m) (The IIDA TESTING SIEVE: 80 mm in bore diameter), and classified with a Ro-Tap sieve shaker (manufactured by IIDA SEISAKUSHO, ES-65 sieve shaker; revolutions per minute: 230 rpm, taps per minute: 130 rpm) for 5 seconds, and the weight (Wc [g]) of the water absorbent agent composition remaining on the meshes and the weight (Wd [g]) of the water absorbent agent composition having passed through the meshes were measured. Then, a moisture absorption blocking ratio (BR) which is a fluidity index at moisture absorption was calculated in accordance with Equation (8) below.
  • BR wt % Wc / Wc + Wd ⁇ 100
  • An amount of Fe (Fe content) was obtained by an ICP (Inductively Coupled Plasma) method in accordance with an analytical curve prepared based on a standard solution.
  • the aqueous monomer solution (1) was poured into a reaction container formed by providing a lid to a 10L stainless double-arm kneader equipped with two sigma vanes and a jacket, and nitrogen gas was injected into the reaction container while keeping a temperature of the reaction solution at 30 °C, so as to carry out replacement with nitrogen in the system.
  • aqueous monomer solution (1) While the aqueous monomer solution (1) was stirred, 2.46 g of sodium persulfate and 0.10 g of L-ascorbic acid each of which serves as a polymerization initiator were separately added to the aqueous monomer solution (1) so that polymerization was started. The polymerization was started approximately 1 min after addition of the polymerization initiator.
  • a resulting hydrous gelatinous crosslinking polymer (1) was polymerized at 30-80 °C while it was crushed, and the hydrous gelatinous crosslinking polymer (1) was taken out after 60 min had elapsed from start of the polymerization.
  • the resulting hydrous gelatinous crosslinking polymer (1) was finely crushed into particles of approximately not more than 5 mm in diameter.
  • the hydrous gelatinous crosslinking polymer (1) thus crushed finely was spread on a wire sheet whose mesh opening size was 300 ⁇ m (50 meshes), and was dried with hot air at 180 °C for 40 min. Then, the resultant was pulverized with a vibrating mill and was further classified and prepared with a JIS standard sieve of 850 ⁇ m in mesh opening size. Through a series of these operations, water absorbent resin powder (1) having a non-uniformly pulverized shape and a weight average particle diameter (D50) of 295 ⁇ m was obtained.
  • D50 weight average particle diameter
  • a surface-crosslinking agent solution containing 0.05 parts by weight of ethyleneglycol diglycidyl ether, 1 part by weight of propylene glycol, 3 parts by weight of water, and 1 part by weight of isopropyl alcohol was evenly mixed with 100 parts by weight of the water absorbent resin powder (1), and the resultant was subjected to a heat treatment at 210 °C for 50 min, so that surface-crosslinked water absorbent resin particles (1) were obtained.
  • the water absorbent resin particles (1) thus obtained had a moisture content of 1 wt%, a CRC of 39 [g/g], an AAP of 28 [g/g], a weight average particle diameter (D50) of 320 ⁇ m, and particles, which are not less than 300 ⁇ m, of 61 wt%.
  • An amount of Fe in a 48 % aqueous solution of sodium hydroxide used for obtaining a sodium acrylate aqueous solution whose neutralization rate was 75 mol% was 0.4 ppm.
  • the water absorbent resin particles (2) thus obtained had a moisture content of 1 wt%, a CRC of 34 [g/g], an AAP of 31 [g/g], a weight average particle size diameter (D50) of 370 ⁇ m, and particles, which are not less than 300 ⁇ m, of 73 wt%.
  • the green tea extract used was an aqueous solution obtained by pulverizing 50 g of generally commercially available green tea into particles which can pass through a standard sieve of 500 ⁇ m, and then putting the particles in 500 g of hot water at approximately 80 °C and extracting an aqueous solution while stirring the particles for 1 hour, and further filtering the aqueous solution.
  • the results of the deodorizing test A on the resulting water absorbent agent composition (1), a stabilization index and a degradable soluble component in the test on stability in maintaining a deodorizing effect of the resulting water absorbent agent composition (1), and the deodorizing test B on an absorbent article (1) are shown in Table 1 (and Tables 3, 5, and 6).
  • a total contained amount of caffeine and catechins in the water absorbent agent composition (1) was 0.3 wt%.
  • the result of measuring an amount of Fe in the resulting water absorbent agent composition (1) is shown in Table 6.
  • An AAP of the water absorbent agent composition (1) was 26 [g/g].
  • the oolong tea extract used was an aqueous solution obtained by pulverizing 50 g of generally commercially available oolong tea into particles which can pass through a standard sieve of 500 ⁇ m, and then putting the particles in 500 g of hot water at approximately 80 °C and extracting an aqueous solution while stirring the particles for 1 hour, and further filtering the aqueous solution.
  • the black tea extract used was an aqueous solution obtained by pulverizing 50 g of generally commercially available black tea into particles which can pass through a standard sieve of 500 ⁇ m, and then putting the particles in 500 g of hot water at approximately 80 °C and extracting an aqueous solution while stirring the particles for 1 hour, and further filtering the aqueous solution.
  • the results of the deodorizing test A on the resulting water absorbent agent composition (5), a stabilization index and a degradable soluble component in the test on stability in maintaining a deodorizing effect of the resulting water absorbent agent composition (5), and the deodorizing test B on an absorbent article (5) are shown in Table 1 (and Table 4).
  • a contained amount of tannin was 0.8 wt%.
  • a moisture absorption blocking ratio (BR) of the water absorbent agent composition (5) was 100 wt%.
  • the pu-erh tea extract used was an aqueous solution obtained by pulverizing 50 g of generally commercially available pu-erh tea into particles which can pass through a standard sieve of 500 ⁇ m, and then putting the particles in 500 g of hot water at approximately 80 °C and extracting an aqueous solution while stirring the particles for 1 hour, and further filtering the aqueous solution.
  • the results of the deodorizing test A on the resulting water absorbent agent composition (11), a stabilization index and a degradable soluble component in the test on stability in maintaining a deodorizing effect of the resulting water absorbent agent composition (11), and the deodorizing test B on an absorbent article (11) are shown in Table 1 (and Tables 3 and 5).
  • a total contained amount of caffeine and catechins in the water absorbent agent composition (11) was 0.008 wt%.
  • An AAP of the water absorbent agent composition (11) was 26 [g/g].
  • the water absorbent resin particles (1) obtained in Production Example 1 were regarded as a comparative water absorbent agent composition (1).
  • the water absorbent agent composition obtained by using the water absorbent resin particles (1) had a moisture content of 2-10 wt%, a CRC of 38-39 [g/g], an AAP of 26-28 [g/g], a weight average particle diameter (D50) of 320-330 ⁇ m, and particles, which are not less than 300 ⁇ m, of 61-63 wt%
  • the water absorbent agent composition obtained by using the water absorbent resin particles (2) had a moisture content of 2-10 wt%, a CRC of 34-35 [g/g], an AAP of 29-30 [g/g], a weight average particle diameter (D50) of 380-390 ⁇ m, and particles, which are not less than 300 ⁇ m, of 75-78 wt%.
  • Comparison of Examples 1-20 and Comparative Examples 1-7 shows that use of the natural ingredient and the temporal deterioration preventing agent in combination allows an improvement in deodorizing performance and a reduction in degradable soluble component. Furthermore, comparison of Examples 1-17 and Examples 18-20 shows more preferable amounts of use of the natural ingredient and the temporal deterioration preventing agent and a more preferable ratio between the natural ingredient and the temporal deterioration preventing agent.
  • the results of the deodorizing test A on the resulting water absorbent agent composition (21), a stabilization index, a degradable soluble component, and an AAP in the test on stability in maintaining a deodorizing effect of the resulting water absorbent agent composition (21), and the deodorizing test B on an absorbent article (21) are shown in Table 3 (and Table 4).
  • a moisture absorption blocking ratio (BR) of the water absorbent agent composition (21) was 100 wt%.
  • Water absorbent resin particles Natural ingredient Temporal deterioration preventing agent Water [wt%] Hydrophilic solvent [wt%] Water absorbent agent composition Physical properties of water absorbent agent composition Absorbent article kind (extract) Added amount [wt%] kind Added amount [ppm] Deodorizing test A Stabilization index [%] Degradable soluble component [wt%] AAP [g/g] Deodorizing test B Ex.1 (1) Green tea 5.0 propyl gallate 100 - - (1) 2.5 100 18 26 2.9 Ex.11 (1) Theaceae plant leaves 0.015 propylparaben 0.1 0.085 - (11) 2.9 97 26 26 2.8 Ex.21 (1) Green tea 5.0 propyl gallate 100 - 0.5 (21) 2.5 100 18 29 2.9 Ex.22 (1) Theaceae plant leaves 0.015 propylparaben 0.1 0.085 0.035 (22) 2.8 100 26 29 2.8 Ex.23 (1) Green tea 5.0 propyl gallate (dry-blended) 100 - - (2
  • the hydrophilic organic solvent (polyol) in addition of the natural ingredient and/or the temporal deterioration preventing agent to the water absorbent resin allows a reduction in damage to powder, so that a reduction in AAP can be prevented.
  • the water absorbent agent composition of the present invention preferably contains polyol.
  • Example 5 To the water absorbent agent composition (5) obtained in Example 5, 0.5 wt% of Reolosil QS-20 (hydrophilic amorphous silica, manufactured by TOKUYAMA) serving as water-insoluble microparticles was mixed evenly, so that a water absorbent agent composition (24) was obtained.
  • Reolosil QS-20 hydrophilic amorphous silica, manufactured by TOKUYAMA
  • Water absorbent resin particles Natural ingredient Temporal deterioration preventing agent Water [wt%] Hydrophilic solvent [wt%] Water insoluble microparticles [wt%] Water absorbent agent composition Physical properties of water absorbent agent composition Absorbent article kind (extract) Added amount [wt%] kind Added amount [ppm] Deodorizi ng test A Stabilization index [%] Degradable soluble component [wt%] BR [wt%] Deodorizin g test B Ex.5 (2) Oolong tea 3.0 sodium erythorbate 50 7.0 - - (5) 2.3 100 21 100 2.6 Ex.21 (1) Green tea 5.0 propyl gallate 100 - 0.5 - (21) 2.5 100 18 100 2.9 Ex.24 (2) Oolong tea 3.0 sodium erythorbate 50 7.0 - 0.5 (24) 2.3 100 21 0 2.6 Ex.25 (1) Green tea 5.0 propyl gallate 100 - 0.5 0.15 (25) 2.5 100 18 0 2.8
  • a water absorbent agent composition (26) was obtained by carrying out the same operation as in Example 1 except that the chelating agent was not added out of the natural ingredient, the temporal deterioration preventing agent, and the chelating agent.
  • a water absorbent agent composition (27) was obtained by carrying out the same operation as in Example 11 except that the chelating agent was not added out of the natural ingredient, the temporal deterioration preventing agent, the chelating agent, and the water.
  • Water absorbent particles Natural ingredient Temporal deterioration preventing agent Water [wt%] Chelating agent aqueous solution [wt%] Water absorbent agent composition Physical properties of water absorbent agent composition Absorbent article kind (extract) Added amount [wt%] kind Added amount [ppm] Deodorizing test A Stabilization index [%] Degradable soluble component [wt%] Deodorizing test B Ex.
  • a comparative water absorbent agent composition (8) was obtained by carrying out the same operation as in Example 1 except that the water absorbent resin particles (1) used in Example 1 were replaced with the water absorbent resin particles (3) obtained in Production Example 3.
  • the amount of Fe in the comparative water absorbent agent composition (8) is mainly the amount of Fe in the water absorbent resin particles (3) which was derived from the 48 % sodium hydrate aqueous solution used to obtain the sodium acrylate aqueous solution whose neutralization rate was 75 mol%.
  • the amounts of Fe in the water absorbent agent compositions (1)-(27) were similar to the amount of Fe in the water absorbent resin particles (1) or (2).
  • a water absorbent agent composition in accordance with the present invention is used as a member constituting an absorbent article.
  • the water absorbent agent composition is used not only for sanitary materials such as an adult paper diaper, a child paper diaper, a sanitary napkin, and an incontinence pad but also for a water stop agent for engineering works and construction, a moisture absorbent, a dehumidifying agent, a water retention agent for agricultural gardening, and the like.

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Claims (12)

  1. Composition d'agent absorbant l'eau comprenant : une résine absorbant l'eau à base (de sel) d'acide polycarboxylique en tant que composant principal ; un ingrédient naturel ; et un agent de prévention de la détérioration dans le temps, dans laquelle ladite composition d'agent absorbant l'eau contient du fer (Fe) en une quantité pas supérieure à 2 ppm, et dans laquelle l'agent de prévention de la détérioration dans le temps est au moins une sorte de composé sélectionné parmi : des agents de réduction hydrosolubles sélectionnés parmi l'acide érythorbique, l'acide L-ascorbique, et des sulfites ; des oxydants hydrosolubles sélectionnés parmi des acides hypochloreux ; des phenylphénols ; l'acide benzoïque ou des esters de celui-ci ; et l'acide hydroxybenzoïque ou des esters de celui-ci, et dans laquelle l'ingrédient naturel est un extrait d'une plante sélectionnée dans le groupe consistant en les Theaceae et les Fagaceae.
  2. Composition d'agent absorbant l'eau selon la revendication 1, dans laquelle :
    l'ingrédient naturel est un ingrédient végétal contenant de la caféine ou des catéchines, ou un ingrédient végétal contenant du tanin ;
    (i) la composition d'agent absorbant l'eau contient l'ingrédient naturel et l'agent de prévention de la détérioration dans le temps en les quantités respectives de 0,01 à 15 % en poids et de 0,05 à 120 ppm (spécifiées par une teneur en matières solides excluant un solvant lorsque l'ingrédient naturel est un extrait), ou
    (ii) la composition d'agent absorbant l'eau contient de la caféine et/ou des catéchines en une quantité totale de 5 ppm à 1 % en poids et l'agent de prévention de la détérioration dans le temps en une quantité de 0,05 à 120 ppm, ou
    (iii) la composition d'agent absorbant l'eau contient du tanin en une quantité de 5 ppm à 1 % en poids et l'agent de prévention de la détérioration dans le temps en une quantité de 0,05 à 120 ppm ; et
    la composition d'agent absorbant l'eau contient l'agent de prévention de la détérioration dans le temps en un rapport en poids de 1/10 à 1/10 000 (spécifié par une teneur en matières solides excluant un solvant lorsque l'ingrédient naturel est un extrait) par rapport à l'ingrédient naturel ou à la caféine et/ou aux catéchines, ou au tanin.
  3. Composition d'agent absorbant l'eau selon la revendication 1 ou 2, dans laquelle la composition d'agent absorbant l'eau a une teneur en humidité de 1 à 15 % en poids.
  4. Composition d'agent absorbant l'eau selon l'une quelconque des revendications 1 à 3, dans laquelle :
    la résine absorbant l'eau à base (de sel) d'acide polycarboxylique est une résine absorbant l'eau à base (de sel) d'acide polyacrylique ayant un taux de neutralisation de 30 à 80 % en moles ;
    la composition d'agent absorbant l'eau se trouve sous la forme de particules ; et
    la composition d'agent absorbant l'eau satisfait en outre à au moins une des propriétés physiques spécifiées par les points (1) à (4) suivants :
    (1) avoir un composant soluble dégradable en une quantité pas supérieure à 40 % en poids ;
    (2) contenir des particules ayant un diamètre des particules (spécifié par un crible standard) supérieur ou égal à 150 µm et inférieur à 850 µm en une quantité supérieure ou égale à 90 % en poids de la composition d'agent absorbant l'eau totale, et contenir des particules ayant un diamètre des particules (spécifié par un crible standard) supérieur ou égal à 300 µm en une quantité supérieure ou égale à 60 % en poids de la composition d'agent absorbant l'eau totale ;
    (3) avoir une capacité d'absorption d'eau sous une charge (AAP) (spécifiée dans ERT 442.2-02) supérieure ou égale à 15 [g/g] ; et
    (4) avoir un taux de blocage d'absorption d'humidité inférieur ou égal à 30 % en poids.
  5. Composition d'agent absorbant l'eau selon l'une quelconque des revendications 1 à 4,
    comprenant en outre un agent chélateur ;
    comprenant en outre des microparticules insolubles dans l'eau ; ou
    comprenant en outre du polyol.
  6. Procédé de production d'une composition d'agent absorbant l'eau, comprenant simultanément ou séparément le mélange d'un ingrédient naturel et d'un agent de prévention de la détérioration dans le temps avec une résine absorbant l'eau qui est un polymère réticulé de monomères insaturés ayant un acide carboxylique et/ou un sel de celui-ci, dans lequel ladite composition d'agent absorbant l'eau contient du fer (Fe) en une quantité inférieure ou égale à 2 ppm, et dans lequel l'agent de prévention de la détérioration dans le temps est au moins une sorte de composé sélectionné parmi : des agents de réduction hydrosolubles sélectionnés parmi l'acide érythorbique, l'acide L-ascorbique, et des sulfites ; des oxydants hydrosolubles sélectionnés parmi des acides hypochloreux ; des phenylphénols ; l'acide benzoïque ou des esters de celui-ci ; et l'acide hydroxybenzoïque ou des esters de celui-ci, et dans lequel l'ingrédient naturel est un extrait d'une plante sélectionnée dans le groupe consistant en les Theaceae et les Fagaceae.
  7. Procédé selon la revendication 6, dans lequel :
    l'ingrédient naturel et l'agent de prévention de la détérioration dans le temps sont mélangés avec la résine absorbant l'eau en les quantités respectives de 0,01 à 15 % en poids et de 0,05 à 120 ppm (spécifiées par une teneur en matières solides excluant un solvant lorsque l'ingrédient naturel est un extrait), et
    la composition d'agent absorbant l'eau contient l'agent de prévention de la détérioration dans le temps en un rapport en poids de 1/10 à 1/10 000 (spécifié par une teneur en matières solides excluant un solvant lorsque l'ingrédient naturel est un extrait) par rapport à l'ingrédient naturel ou à la caféine et/ou aux catéchines, ou au tanin.
  8. Procédé selon l'une quelconque des revendications 6 ou 7, dans lequel la composition d'agent absorbant l'eau a une teneur en humidité de 1 à 15 % en poids.
  9. Emballage d'agent absorbant l'eau comprenant un récipient scellé rempli d'une composition d'agent absorbant l'eau décrite dans l'une quelconque des revendications 1 à 5.
  10. Procédé de conservation ou de stockage comprenant la conservation d'un emballage d'agent absorbant l'eau décrit dans la revendication 9 dans un état emballé pendant au moins 30 jours jusqu'à ce que l'emballage d'agent absorbant l'eau soit en fait utilisé.
  11. Procédé de conservation ou de stockage comprenant la conservation d'un article absorbant emballé pour l'absorption d'urine dans un état emballé pendant au moins 30 jours jusqu'à ce que l'article absorbant emballé pour l'absorption d'urine soit véritablement utilisé, l'article absorbant emballé pour l'absorption d'urine contenant une composition d'agent absorbant l'eau décrite dans l'une quelconque des revendications 1 à 5.
  12. Procédé de production d'un article absorbant comprenant la production d'un article absorbant pour l'absorption d'urine en utilisant une composition d'agent absorbant l'eau contenant : une résine absorbant l'eau emballée en tant que composant principal ; et un ingrédient naturel, la composition d'agent absorbant l'eau contenant en outre un agent de prévention de la détérioration dans le temps, dans lequel ladite composition d'agent absorbant l'eau contient du fer (Fe) en une quantité pas supérieure à 2 ppm, et dans lequel l'agent de prévention de la détérioration dans le temps est au moins une sorte de composé sélectionné parmi : des agents de réduction hydrosolubles sélectionnés parmi l'acide érythorbique, l'acide L-ascorbique, et les sulfites ; des oxydants hydrosolubles sélectionnés parmi des acides hypochloreux ; des phenylphénols ; l'acide benzoïque ou des esters de celui-ci ; et l'acide hydroxybenzoïque ou des esters de celui-ci, et dans lequel l'ingrédient naturel est un extrait d'une plante sélectionnée dans le groupe consistant en les Theaceae et les Fagaceae.
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